CN101516382A - Cationic latex as a carrier for bioactive ingredients and methods for making and using the same - Google Patents

Cationic latex as a carrier for bioactive ingredients and methods for making and using the same Download PDF

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CN101516382A
CN101516382A CN 200780034318 CN200780034318A CN101516382A CN 101516382 A CN101516382 A CN 101516382A CN 200780034318 CN200780034318 CN 200780034318 CN 200780034318 A CN200780034318 A CN 200780034318A CN 101516382 A CN101516382 A CN 101516382A
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monomer
yue
cationic polymer
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V·克里施南
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马拉德克里科聚合物公司
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/70Carbohydrates; Sugars; Derivatives thereof
    • A61K31/715Polysaccharides, i.e. having more than five saccharide radicals attached to each other by glycosidic linkages; Derivatives thereof, e.g. ethers, esters
    • A61K31/716Glucans
    • A61K31/722Chitin, chitosan
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10Macromolecular compounds
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES, AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL, OR TOILET PURPOSES
    • A61K31/00Medicinal preparations containing organic active ingredients
    • A61K31/70Carbohydrates; Sugars; Derivatives thereof
    • A61K31/7042Compounds having saccharide radicals and heterocyclic rings
    • A61K31/7048Compounds having saccharide radicals and heterocyclic rings having oxygen as a ring hetero atom, e.g. leucoglucosan, hesperidin, erythromycin, nystatin digitoxin or digoxin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/34Esters containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00Post-polymerisation treatments
    • C08F6/001Removal of residual monomers by physical means
    • C08F6/003Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/26Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F2220/285Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing an ether chain in the alcohol moiety
    • C08F2220/286Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing an ether chain in the alcohol moiety and containing polyethylenoxide in the alcohol moiety

Abstract

This invention relates to latex compositions that incorporate at least one bioactive component such as an antibacterial or antifungal agent, and methods for making and using such latex compositions. The latex compositions disclosed herein can be prepared by the emulsion polymerization of the latex component monomers in the presence of the at least one bioactive component.

Description

作为生物活性成分的载体的阳离子型胶乳及其生产和使用方法 As a carrier of biologically active ingredient cationic latex and its production and use

技术领域 FIELD

本发明涉及可以与各种基材(例如,纺织品、金属、纤维素材料、 塑料等)组合使用的聚合物材料的领域,并且涉及生物活性物质/抗微生物剂(例如,抗菌剂和抗真菌剂材料)的领域。 The present invention relates to the field of various substrates (e.g., textiles, metal, cellulosic materials, plastics, etc.) used in combination with polymer material, and to a biologically active substance / agent, an antimicrobial (e.g., antibacterial and antifungal agents art material).

背景技术 Background technique

一直利用将胶乳聚合物涂料沉积在固体基材上来赋予那些基材以某些产品使用性能,例如,疏水性、强度、粘合性质、相容性等。 The latex polymer coating has been deposited using a solid substrate onto a substrate to impart those properties of certain products, e.g., hydrophobicity, strength, adhesive properties, compatibility, and the like. 根据起始的单体、表面活性剂、乳液聚合条件和其它参数的选择,沉积的聚合物可以被设计用来携带阴离子型、阳离子型、或两性的电荷, 这是一个直接影响涂层性能的特征。 The selection of the starting monomers, surfactants, emulsion polymerization conditions and other parameters, the deposited polymers can be designed to carry an anionic, cationic, or amphoteric charge, from a direct affect coating properties feature. 另外,得到的胶乳聚合物可以与多种其它功能材料共混,以赋予最终的涂层材料以另外的或增强的特征。 Further, the resulting latex polymer can be blended with a variety of other functional materials to impart additional final coating material to or enhanced features.

在美国专利申请公布2005/0003163中公开的阳离子型胶乳聚合物所表现出的一个特别有用的特征是它们固有的抗微生物特征。 In U.S. Patent Application Publication 2005/0003163 in the cationic latex polymers disclosed it exhibited a particularly useful feature is their inherent antimicrobial characteristics. 阳离子型聚合物还可以与包含小分子生物活性化合物(更典型地与抗微生物活性相关的物质)的组合物共混,以便增强这些性能。 Cationic polymer blend composition may further comprise a small molecule with a biologically active compound (more typically associated with antimicrobial activity material), in order to enhance these properties. 这些抗微生物组分通常以相对小的量使用,在已经生产聚合物之后作为制剂成分加入。 These antimicrobial components are usually used in relatively small amounts, as a formulation component was added after the polymer has been produced. 尽管这种混合物是有用的,但是在试图增强或控制这些组合物可能提供的抗微生物保护的程度方面仍有许多实际的问题。 Although this mixture is useful, but in an attempt to enhance or control are still many practical problems the extent of antimicrobial protection aspects of these compositions may provide. 例如,这种组合物和方法对于为材料提供长期保护通常是不充分的,特别是其抗真菌性能。 For example, such compositions and methods for providing long-term protection of materials are generally inadequate, particularly their anti-fungal properties. 还需要增加抗微生物性能或更精细地控制抗微生物性能的方法。 Also we need to increase the antimicrobial properties or finer control method antimicrobial properties. 与引入新的抗微生物材料(也就是聚合物)有关的管理问题可能是显著的。 Management issues related to the introduction of new antimicrobial material (ie, polymer) may be significant. 此外,仍难以得到延长或扩展抗微生物性能的有效性的方法。 Further, still difficult to obtain the effectiveness of prolonged or extended antimicrobial properties.

因此,所需要的是赋予胶乳聚合物以及由其制备的涂层和制品以抗微生物活性和增强其抗微生物活性的新的方法和途径。 Accordingly, what is needed is a latex polymeric coatings and articles prepared therefrom, and to enhance its antimicrobial activity and new methods and approaches to impart antimicrobial activity. 还需要的是更密切地控制这种材料的抗微生物活性的方法,包括扩展其生物活性有效性的方法。 What is also needed is a method of antimicrobial activity more closely controlled such materials, including bioactive expand its effectiveness.

发明内容 SUMMARY

本发明包括用于将生物活性成分或抗微生物成分例如抗细菌剂和抗真菌剂并入到胶乳中以便可以增强和控制胶乳的抗微生物性能的新的方法和途径。 The present invention includes biologically active ingredients or antimicrobial ingredients such as antibacterial agents and antifungal agents can be incorporated into the latex so as to enhance control and new methods and approaches latex antimicrobial properties. 本发明还涉及新型的生物活性的阳离子型聚合物胶乳材料。 The present invention also relates to novel cationic polymer latex materials biological activity. 在一个方面中,本发明提供了在乳液聚合工艺过程中将抗微生物成分并入到胶乳中的方法。 In one aspect, the present invention provides a method of an antimicrobial component incorporated in the emulsion polymerization process to latex. 以前,在聚合过程之后已经将抗微生物剂加入到胶乳中,并且是作为用于胶乳制品或用于最终用途应用例如油漆的防腐剂以相对小的量加入的。 Previously, after the polymerization process has been added to the antimicrobial agent to the latex, and latex products or used as end use applications such as paint preservative added in relatively small amounts. 本发明允许使用较高浓度的各种生物活性成分,包括高疏水性的生物活性成分,其可以容易地被并入到胶乳中,使得得到的胶乳粒子作为活性成分的载体起作用。 The present invention allows the use of higher concentrations of various biological active ingredients, including highly hydrophobic bioactive components, which can be easily incorporated into the latex in the latex particles so obtained functions as a carrier of the active ingredient. 用这样的方式全面地并入活性成分可以提供添加剂的实质上均勻的分布并且产生与以前制造的分散体相比优异和持续的性能。 Fully incorporated active ingredient in this manner can provide a substantially uniform distribution of the additive and dispersion compared to the previous generation of producing excellent and sustained performance.

在本发明的一个方面中,进行乳液聚合,使得生物活性剂在乳液聚合过程中被并入到聚合物中,典型地是通过将生物活性组分溶解在单体流中进行的。 In one aspect of the present invention, emulsion polymerization, such that the bioactive agent is incorporated into the polymer during emulsion polymerization, typically is performed by the bioactive component dissolved in the monomer stream. 用这样的方式,生物活性剂可以被至少部分地包封在胶乳聚合物基质内。 In this manner, the bioactive agent may be at least partially encapsulated within the latex polymer matrix. 这种方法提供的一个优点在于能够并入或包封大量的生物活性成分,包括疏水性组分,不会使生物活性剂显著地降解。 One advantage of this method is the ability to provide a large amount of incorporated or encapsulated biologically active ingredients, including hydrophobic components, without biologically active agent is significantly degraded. 在另一个方面中,本发明还提供以具有一些固有的抗微生物性能的阳离子型胶乳为基础的可调的抗微生物系统,所述阳离子型胶乳还作为至少一种生物活性成分的载体起作用,并且任选地另外包括可以与本文中公开的胶乳共混的另一种生物活性填加剂。 In another aspect, the present invention has also provided some inherent antimicrobial properties against the cationic antimicrobial latex adjustable based system, the cationic latex also acts as a carrier at least one bioactive ingredient, and optionally further comprising another biologically active additive filled latex may be blended with the disclosure herein. 因此,这些胶乳可以用于多功能的目的,例如除了作为活性功能成分的载体之外还提供结合、强度、和分散性能,并且任选地构成共混的抗微生物组合物的一个组分。 Thus, these latexes may be used for multi-functional purposes, for example as a carrier in addition to the active ingredient also provides a binding function, strength, and dispersion properties, and optionally constituting one component of the antimicrobial composition blended.

在一个方面中,因为生物活性成分典型地在乳液聚合工艺过程中被并入到胶乳中,这些生物活性组分可以至少部分地被包封在胶乳聚合物基质内。 In one aspect, the biologically active ingredient as an emulsion polymerization process typically are incorporated into the latex, these bioactive components may be at least partially encapsulated within the latex polymer matrix. 在另一个方面中,生物活性组分可以实质上被包封在胶乳聚合物基质内。 In another aspect, the bioactive component can be substantially encapsulated within the latex polymer matrix. 尽管不希望束缚于理论,但是认为通过为期望的最终用途应用递送活性成分,具有包封的生物活性成分的胶乳聚合物可以对利用这种胶乳聚合物的环境提供维持和受控的生物活性成分的暴露,从而对产品或应用提供更长和更有效的的保护。 While not wishing to be bound by theory, it is believed that by delivering the active ingredient to a desired end use application, the latex having a polymer encapsulated bioactive ingredient and may be provided to maintain a controlled environment on the use of such latex polymer bioactive ingredient exposure, thus providing a longer and more effective protection for the product or application. 此外,因为生物活性阳离子型胶乳可以由现有的乳液聚合工艺形成,该聚合方法有利地允许制备高分子聚合物。 Further, since the bioactive cationic latex can be formed by a conventional emulsion polymerization process, the polymerization process advantageously allows the preparation of polymers.

在另一个方面中,本文中公开的方法还提供一种可能性,即,使用调配抗^t生物剂的方法的组合来调节抗微生物性能以配置抗微生物剂的可能性。 In another aspect, the methods disclosed herein also provide a possibility, i.e., a combination of an anti-^ t formulated using biological agents adjusting method of configuration possibilities to antimicrobial properties of the antimicrobial agent. 例如,可以通过在乳液聚合工艺过程中将生物活性成分并入到胶乳中和将得到的胶乳制品与混合物中的相同或不同的生物活性组分组合来赋予产品以高度定制的抗微生物性能。 For example, by the bioactive component will be incorporated into a latex during the emulsion polymerization process and the resultant gum composition components dairy products to impart the same or different bioactive mixtures with a highly customized antimicrobial properties. 这种方法允许根据期望的环境和性能使用聚合物、添加剂、或其二者来选择和调节抗微生物性能。 This approach allows the use of polymer additives, or both depending on the environment and the desired properties of the selected and adjusted to antimicrobial properties.

在另一个方面中,本文中公开的技术可以提供与标准方法相比将更大量的活性成分包封在胶乳配合物中的能力。 In another aspect, the techniques disclosed herein may provide the ability compared to the standard method of a greater amount of the active ingredient encapsulated in the latex of the complex. 例如,在已经制备胶乳聚合物之后,抗微生物組分通常以相对小的量用作制剂成分,并且 For example, after the polymer latex has been prepared, the antimicrobial components are usually used in relatively small amounts of the formulation components, and

这种生物活性典型地是以最大约1000-2000 ppm的浓度范围使用。 Such biological activity most typically in a concentration range of about 1000-2000 ppm is used. 相比之下,本发明的胶乳配合物的抗微生物组分可以以基于总的单体重量为高达约40重量%的浓度使用。 In contrast, the antimicrobial component of the latex of the present invention may be complex based on the total weight of monomers up to a concentration of about 40% by weight is used. 在这个方面中,本发明可以提供稳定的、浓缩的分散体,其可以直接使用,或者作为添加剂,或作为可以被稀释并且加入到需要抗微生物保护的其它系统中的浓缩的分散 In this aspect, the present invention can provide stable, concentrated dispersions that can be used directly or as an additive, or as a concentrate can be diluted and added to other systems requiring antimicrobial protection in the dispersion

体。 body. 高的抗微生物组分浓度提供灵活性并且确保了这些胶乳组合物作为浓缩物以及以非浓缩形式的应用。 High antimicrobial component concentrations provide flexibility and ensure that these latex compositions as concentrates and applied in a non-concentrated form.

尽管本文中公开的方法可以应用于特定的最终用途需要的任何生物活性剂,但是本发明主要涉及提供或增强胶乳、基材、或特定的最终产品的抗微生物性能。 While the methods disclosed herein may be applied to any biologically active agent required for particular end use, but the present invention is directed primarily to provide or enhance the antimicrobial properties of latex, substrate, or particular end product. 相关的抗微生物活性可以包括抗细菌活性、 抗真菌活性、抗病毒活性、抗寄生虫活性、或其任何组合,这取决于生物活性剂的特定选择。 Related antimicrobial activity may comprise antibacterial activity, antifungal activity, antiviral activity, antiparasitic activity, or any combination thereof, depending on the particular selection of bioactive agents. 如本文中使用的,术语"生物活性"组分、 试剂、或成分与"抗微生物"组分、试剂、或成分可互换地使用。 As used herein, the term "biologically active" component, reagent, or composition of "antimicrobial" component, reagent, or composition used interchangeably.

在另一个方面中,本发明提供生物活性的阳离子型聚合物胶乳, In another aspect, the present invention provides a bioactive cationic polymer latex, and

其包括: Including:

a) 包括以下聚合产物的胶乳聚合物,所述聚合产物为:i)至少一种烯属不饱和的第一单体和H)至少一种烯属不饱和的第二单体(所述第二单体是阳离子型的,或者是阳离子的前体)的聚合产物; a) a latex polymer comprising the polymerization product, the polymerization product of: i) at least one ethylenically unsaturated first monomer and H) at least one ethylenically unsaturated second monomer (the first two monomer is cationic or a precursor cationic) polymerization product;

b) 至少部分地包封在胶乳聚合物内的至少一种生物活性组分;和 b) at least partially enclosing the at least one biologically active component within the latex polymer; and

c) 任选的被并入到胶乳聚合物中的至少一种空间体积大的组分。 c) it is optionally incorporated into the latex polymer of at least one sterically bulky component. 在这个方面,可以使用各种重量百分数的烯属不饱和的第一单体 In this regard, a variety of weight percent of the first ethylenically unsaturated monomer

和烯属不饱和的第二单体(其为阳离子型的或者是阳离子前体,可以被称为"阳离子型"单体)。 And a second ethylenically unsaturated monomer (which is a cationic or cation precursor, may be referred to as "cationic" monomer). 例如,胶乳可以包括基于总的单体重量为约0. 01-约75重量%的阳离子型第二单体。 For example, the latex may comprise based on the total monomer weight of about 0.5 wt% to about 75 01- cationic second monomer.

还在这个方面中,尽管被并入到胶乳聚合物中的至少一种空间体积大的组分是任选的组分,但是本发明还提供了使用这种组分的不同的量和浓度。 Also in this regard, although the large latex polymer is incorporated into the volume of space of at least one component is an optional component, but the present invention also provides a use of different amounts and concentrations of such components. 因此,如本领域技术人员理解的,在不包括至少一种空间体积大的组分的生物活性阳离子型聚合物胶乳中,可以通过增加阳离子型第二单体的相对比例、通过添加表面活性剂例如非离子型表面活性剂和类似物质、包括这些方法的任何組合来增强胶乳稳定性。 Thus, as appreciated by those skilled in the art, the bioactive cationic polymer latex does not comprise at least one sterically bulky component, by increasing the relative proportion of the cationic second monomer, by the addition of a surfactant for example, nonionic surfactants and the like, including any combination of these methods to enhance the latex stability. 在存在有至少一种空间体积大的组分的情况下,可以降低阳离子型第二单体的相对比例和/或可以不含表面活性剂。 In the presence of at least one sterically bulky component, the relative proportions may be reduced cationic second monomer and / or may not contain a surfactant.

另外,本发明的胶乳还可以包括被并入到阳离子型聚合物胶乳中的空间体积大的组分,用来空间上稳定该胶乳。 Further, the latex of the present invention may be incorporated into the space further comprises a cationic polymer latex in a large volume component, for stabilization of the latex on the space. 这些空间体积大的组分可以包括但不限于以下所述的单体、聚合物、及其混合物。 These spaces bulky components can include, but are not limited to the monomers, polymers, and mixtures thereof. 因此, 可以将单体作为共聚单体并入,其可以连接于阳离子型聚合物的主链 Thus, it can be incorporated as a comonomer, which can be connected to the main chain of a cationic polymer

或者构成阳离子型聚合物主链的一部分,其实例包括烷氧基化的烯属不饱和的第三单体。 Cationic or form part of the polymer backbone, examples of which include an alkoxylated ethylenically unsaturated third monomer. 可以通过吸附或接枝到胶乳表面来并入聚合物,其实例包括聚乙烯醇。 May be incorporated into the polymer by adsorption or grafted onto the latex surface, examples thereof include polyvinyl alcohol.

在另一个方面中,本发明提供生产生物活性阳离子型聚合物胶乳 In another aspect, the present invention provides the production of a bioactive cationic polymer latex

組合物的乳液聚合:",。、.,、 The composition of the emulsion: ', ,,.

a) 至少一种烯属不饱和的第一单体; a) at least one ethylenically unsaturated first monomer;

b) 至少一种烯属不饱和的笫二单体,其为阳离子型的或者是阳离子的前体; b) at least one ethylenically unsaturated monomer undertaking of two, which is cationic or a precursor to a cation;

c) 至少一种生物活性组分; c) at least one bioactive component;

d) 至少一种自由基引发剂; d) at least one free radical initiator;

e) 任选的至少一种空间体积大的烯属不饱和的第三单体; e) optionally at least one sterically bulky ethylenically unsaturated third monomer;

f) 任选的至少一种空间体积大的聚合物;和 f) optionally at least one sterically bulky polymer; and

g) 任选的至少一种非离子型表面活性剂。 g) optionally at least one non-ionic surfactant.

因此,在一个方面中,可以在乳液聚合工艺过程中的任何时间将至少一种生物活性组分溶解于单体原料中。 Accordingly, in one aspect, any time during the emulsion polymerization process of at least one biologically active ingredient is dissolved in the monomer feed. 另外,在另一个方面中, 可以在引发乳液聚合之前将含水组合物组分和至少一种生物活性组分作为分散体提供。 Further, in another aspect, the composition may be aqueous component and at least one biologically active components are provided in a dispersion prior to initiating the emulsion polymerization. 因此,本发明提供分批工艺,其中在种子阶段(seed stage)存在有至少一种生物活性组分。 Accordingly, the present invention provides a batch process wherein the seed stage (seed stage) there is at least one biologically active component. 在这个方面中,在包括至少一 In this aspect, at least comprising a

发乳液聚合。 Fat emulsion polymerization. 另外,本发明还提供半连续工艺,其中在組合物的并非所有组分都从开始时就都存在的情况下引发乳液聚合,而是有一些在引发聚合之后的不同时间加入。 Further, the present invention also provides a semi-continuous process, wherein the polymerization initiator in a case where not all the components of the composition are from at the outset are present, but there are added at different times after the initiation of the polymerization. 在这个方面,例如可以在种子阶段之后的任何时间加入至少一种生物活性组分。 In this regard, for example, adding at least one bioactive component at any time after the seed stage. 在另一个方面中,例如, 可以在接种期之后的任何时间加入上述提供的任何其它组分或组分的组合,除了乳液聚合的引发和扩散所需的任何组分的总量的至少一部分之外。 In combination with any other component or components in another aspect, for example, may be added provided above at any time after inoculation period, in addition to the total amount of any component of the polymerization initiator and at least a portion of the diffusion required outer. 因此,本文中提供的生物活性阳离子型胶乳可以通过任何多种分批工艺或通过半连续工艺来生产。 Thus, the biological activity provided herein or cationic latexes may be produced by any of a variety of semi-batch process by a continuous process. 例如,至少一种生物活性组分;。 For example, at least one bioactive component;. 、 曰、 p 、 、. ) , Saying, p,,.)

在一个方面中,本发明的生物活性胶乳可以以涂层提供或者作为涂层使用,其可以应用于医学植入物,包括人造的球窝关节、榛条体、 支架、牙科植入物、销钉、螺钉、导管等。 In one aspect, the bioactive latex of the present invention may be provided as a coating or as a coating which may be applied to medical implants, including artificial ball and socket joint, hazel strip body, stents, dental implants, pins , screws, catheters and the like. 这种涂层还可以提供在日常的表面上,例如空调的线圏、空气过滤器、管道、屋顶、浴室物品、 厨房物品等。 Such a coating may also be provided on everyday surfaces, such as wire rings of the air conditioner, air filters, pipes, roofing, bathroom items, kitchen items and the like. 这种涂层可以防止交通工具以及家庭、医院、和其它建筑物中的微生物感染,例如细菌和霉菌。 This coating prevents microbial vehicles and homes, hospitals, and other buildings of infection, such as bacteria and fungi. 最终产品的应用的另外的实 In addition the real application of the final product

例是作为水溶液或直接以粉末形式使用,例如用于为冷却水循环灭菌; 或者用于间接的用途,例如通过添加到油漆或其它表面涂层中。 Embodiment is in powder form or as an aqueous solution to be used directly, for example for cooling water circulation sterilization; or for indirect use, for example by addition to paints or other surface coatings.

本发明的这些和其它特征、方面、实施方案、和优点会在考察以下的发明详述之后变得显而易见。 The present invention These and other features, aspects, embodiments, and advantages will become apparent from the following detailed description of the invention, the following investigation. 然而,应该理解,提供这些方面、 实施方案、和实施例只是用于说明性的目的,而不应该以任何方式将其看作是对本发明的范围的限制。 However, it should be understood that these aspects, embodiments, and examples are for illustrative purposes, and should not in any way be considered as limiting the scope of the present invention.

附图说明 BRIEF DESCRIPTION

图l是表示使用ASTMG21评价涂布在牛皮纸上的各种抗微生物胶乳的抗微生物性能的图。 Figure l is a diagram of FIG antimicrobial properties evaluated using ASTMG21 coated on kraft various antimicrobial latexes.

图2是表示30-111真菌试验的结果,所述试验基于形成干燥胶乳的1" X 1"薄片,将真菌直接接种在样品上,然后在7天后观察其生长情况的图。 FIG. 2 shows the results of the test fungi 30-111, based on said test sheet to form a dried latex 1 "X 1", the direct inoculation of fungi on the sample and then observing its growth in FIG. 7 days.

图3是表示涂层的纸样品的第二轮试验的结果的图,是根据ASTM D-3273在28天的时间内进行试验的。 FIG 3 is a graph showing the results of a second round of testing of coated paper samples, tests are carried out in 28 days in accordance with ASTM D-3273. 在这项研究中,不是将真菌直接接种在表面上,而是将其作为孢子保持在湿度试验室中,然后将其落在涂层纸的表面上。 In this study, the fungus is not directly inoculated on the surface, but it is kept in a humidity chamber as spores, then it falls on the surface of the coated paper.

图4是表示与涂层纸相比,使用ASTMD-3273评价在湿部工艺(wet end process)中将抗微生物胶乳并入到纸中的纸的抗微生物性能的图。 FIG 4 is a diagram compared with coated paper, using ASTMD-3273 evaluation unit in a wet process (wet end process) will be incorporated into an antimicrobial latex FIG antimicrobial properties of paper of the paper.

具体实施方式 detailed description

本发明提供可用于与各种基材(例如,纺织品、金属、纤维素材料、 塑料、等等)组合使用的新的胶乳聚合物材料,其中所述聚合物材料包物中的生物活性组分。 The present invention provides new latex polymeric materials for various substrates (e.g., textiles, metal, cellulosic materials, plastics, etc.) for use in combination, wherein the biologically active component of the inclusions in the polymer material . 本发明还提供允许在乳液聚合过程中并入高浓度的活性成分(例如,抗真菌剂)的新的方法和工艺。 The present invention provides also allows the incorporation of high concentrations of active ingredients in the emulsion polymerization process (e.g., antifungal agents) new methods and processes. 在一个方面中,例如,公开的工艺可用于在乳液聚合过程中并入 In one aspect, for example, disclosed process may be used incorporated in the emulsion polymerization process

基于总的单体重量(单体的"phm"或份数百分比)为约0. 01%-约40% 的显著疏水性的生物活性成分。 About 40% of the active ingredient biologically significant hydrophobicity - based on the total weight of monomers ( "phm" fraction or percentage of monomer) is about 0.01%. 尽管生物活性成分可以在聚合工艺过程中的任何阶段引入,包括在种子形成阶段的非常早的阶段,但是在一个方面中,可以在聚合过程的较后阶段过程中添加生物活性组分或添加剂(生物添加剂),例如在已经将约30%-约90%的单体进料到聚合反应器中时添加。 Although the biologically active ingredient can be introduced at any stage of the polymerization process including very early stage in the seed formation stage, in one aspect, the bioactive component may be added at a later stage or additives during the polymerization process ( biological additives), for example, has about 30% - about 90% of the added monomers fed to the polymerization reactor.

有用的生物活性添加剂可以是固体、液体、或其组合。 Useful biologically active additives can be solids, liquids, or combinations thereof. 可以用于本发明的许多生物活性添加剂是实质上水不溶性的或者具有有限的水中溶解度。 Many biologically active additives can be used in the present invention are substantially water insoluble or have limited solubility in water. 在这个方面,典型的水不溶性的、疏水性的生物活性剂可以溶解于在乳液聚合中所用的至少一种单体中。 In this aspect, the typical water insoluble, hydrophobic bioactive agent may be dissolved in at least one of the monomers used in the emulsion polymerization. 因此,典型的疏水性 Thus, a typical hydrophobic

原料中而被引二到聚合反应:中:因此,、4择用^ i予抗微生物性能 Two feedstock is introduced to the polymerization: in which: Thus ,, ^ i I 4 Optional with antimicrobial properties

的典型的成分通常可溶解于用于生产聚合物胶乳的单体中。 Typical ingredients are typically soluble in the polymer latex used in the production of monomer. 在另一个方面中,在本发明中有用的生物活性添加剂也可以是实质上水溶性的, 其实例包括邻苯基苯酚盐(o-pheny 1 phena te ,去除质子化的邻苯基苯酚)、和类似的试剂。 In another aspect, the present invention is useful in the biologically active additive may be a substantially water soluble, and examples thereof include o-phenyl phenate (o-pheny 1 phena te, deprotonated o-phenylphenol), and similar agents. 在这个方面中,不需要这种亲水性的生物活性填加剂可溶解于要聚合的任何单体中。 In this regard, no such hydrophilic bioactive filling additives may be dissolved in any of the monomers to be polymerized.

在另一个方面中,不需要抗微生物成分可溶解于所用的至少一种单体中,因为这些成分也可以作为预制的水中分散体加入。 In another aspect, the antimicrobial component does not need to be dissolved in at least one of the monomers used, as these ingredients can also be added as a preformed dispersion in water. 在这个方面中,可以通过使用相对浓缩的量的添加剂并且使用表面活性剂、分散剂等分散,并且典型地采用诸如高速搅拌器、匀化器、Eppenbach 混合器、或类似装置的混合装置来生产分散体,也可采用其它方法来生产。 In this aspect, by using a relatively concentrated amount of an additive and a surfactant, dispersing agent dispersion, and typically employed as a high-speed stirrer, a homogenizer, an Eppenbach mixer, or the like mixing device to produce dispersion, other methods may also be produced. 在这种情况下,可以将分散体进料到反应器中,以将适当量的活性成分递送到胶乳中。 In this case, the dispersion can be fed to the reactor in order to deliver an appropriate amount of active ingredient to the latex.

在一个方面中,本发明包括生物活性的阳离子型聚合物胶乳,其包括:a) 包括以下聚合产物的胶乳聚合物,所述聚合产物为:i)至少一种烯属不饱和的第一单体和ii)至少一种烯属不饱和的第二单体(所述第二单体是阳离子型的,或者是阳离子的前体)的聚合产物; In one aspect, the present invention comprises a bioactive cationic polymer latex comprising: a) a latex polymer comprising the polymerization product, the polymerization product of: i) at least one ethylenically unsaturated first single body and ii) at least one ethylenically unsaturated second monomer (the second monomer is cationic or a precursor cationic) polymerization product;

b) 至少部分地包封在胶乳聚合物内的至少一种生物活性组分;和 b) at least partially enclosing the at least one biologically active component within the latex polymer; and

c) 任选的被并入到胶乳聚合物中的至少一种空间体积大的组分。 c) it is optionally incorporated into the latex polymer of at least one sterically bulky component. 如本文中提供的,被并入到胶乳聚合物中的至少一种空间体积大 As provided herein, it is incorporated into the latex polymer of at least one sterically bulky

的组分可以独立地选自至少一种空间体积大的烯属不饱和的第三单体、至少一种空间体积大的聚合物、或其任何组合。 The component may be independently selected from at least one sterically bulky ethylenically unsaturated third monomer, at least one sterically large volume of the polymer, or any combination thereof. 在本文中考虑了这些组分中的每一种、以及任选的或另外的组分。 Each considered, and optionally additional components or these components herein.

在另一个方面中,本发明还包括生产生物活性阳离子型聚合物胶乳的方法,包括引发含水组合物的乳液聚合,所述含水组合物在乳液聚合过程中的任何时间包括以下组分: In another aspect, the present invention further comprises a method of producing a bioactive cationic polymer latex comprising emulsion polymerization initiator aqueous composition, the aqueous composition at any time during the emulsion polymerization process include the following components:

a) 至少一种烯属不饱和的第一单体; a) at least one ethylenically unsaturated first monomer;

b) 至少一种烯属不饱和的第二单体,其为阳离子型的或者是阳离子的前体; b) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation;

c) 至少一种生物活性组分; c) at least one bioactive component;

d) 至少一种自由基引发剂; d) at least one free radical initiator;

e) 任选的至少一种空间体积大的烯属不饱和的第三单体; e) optionally at least one sterically bulky ethylenically unsaturated third monomer;

f) 任选的至少一种空间体积大的聚合物;和 f) optionally at least one sterically bulky polymer; and

g) 任选的至少一种非离子型表面活性剂。 g) optionally at least one non-ionic surfactant.

在又一个方面中,本发明提供生产生物活性的阳离子型聚合物胶乳的方法,其包括: In yet another aspect, the present invention provides a cationic polymer latex produced biological activity, comprising:

a)提供含水组合物,所述含水组合物包括: a) providing an aqueous composition, said aqueous composition comprising:

i) 至少一种烯属不饱和的第一单体; i) at least one ethylenically unsaturated first monomer;

ii) 至少一种烯属不饱和的第二单体,其为阳离子型的或者是阳离子的前体; ii) at least one ethylenically unsaturated second monomer that is cationic or a precursor to a cation;

iii) 任选的至少一种空间体积大的烯属不饱和的第三单体; iii) optionally at least one sterically bulky ethylenically unsaturated third monomer;

iv) 至少一种自由基引发剂;和 iv) at least one free radical initiator; and

v) 任选的至少一种非离子型表面活性剂;b) 引发该组合物的乳液聚合;和 v) optionally at least one non-ionic surfactant; b) the polymerization initiator composition; and

c) 在乳液聚合工艺过程中向组合物中添加至少一种生物活性组分。 c) adding at least one bioactive component to the composition during the emulsion polymerization process.

可以用作烯属不饱和的第一单体、烯属不饱和的第二单体、和空间体积大的组分的许多化合物和物质公开在欧洲专利EP 1109845和相应的PCT公布的专利申请WO 00/8008077中,其各自的公开被全文并入本文作为参考。 It can be used as ethylenically unsaturated first monomers, ethylenically unsaturated second monomer, and a large volume of space and the material composition of many of the compounds disclosed in European Patent No. EP 1109845 and corresponding Patent Publication PCT Application WO 00/8008077, the disclosure of each of which are incorporated herein by reference.

烯属不饱和的第一单体 A first ethylenically unsaturated monomer

可以在本发明的胶乳中使用各种烯属不饱和的第一单体。 Using various ethylenically unsaturated first monomer in the latex of the present invention. 在一个方面中,烯属不饱和的第一单体可以是非阳离子型的。 In one aspect, ethylenically unsaturated first monomers can be non-cationic. 适合的单体的实例可以至少在都属于Krishnan的美国专利5, 830, 934、美国专利申请公布2005/0065284和2005/0003163、和欧洲专利EP 1109845中找到,其各自的公开内容被全文并入本文作为参考。 Examples of suitable monomers may belong to Krishnan at least in U.S. Patent 5, 830, 934, U.S. Patent Application Publication 2005/0065284 and 2005/0003163, and European Patent No. EP 1109845 found, the respective disclosure of which is incorporated herein by reference. 在这个方面中,这种单体的实例包括但不限于乙烯基芳香族单体、卣化或非卣化的烯烃 In this aspect, examples of such monomers include, but are not limited to, vinyl aromatic monomers, wine container of wine container or olefins

单体、脂肪族的共轭二烯单体、非芳香族的不饱和的单或二羧酸酯单体、基于不饱和的二羧酸单体的半酯的单体、不饱和的单或二羧酸单体、含氮单体、含腈单体、环状或无环的含胺单体、支化或非支化的烷基乙烯基酯单体、卣化的或非卣化的烷基丙烯酸酯单体、囟化或非囟化的芳基丙烯酸酯单体、羧酸乙烯基酯、乙酸烯基酯、羧酸烯基酯、 乙烯基卤化物、偏卤乙烯(vinyl idenehalide)、或其任何组合,其任一种具有最多20个碳原子。 Monomers, aliphatic conjugated diene monomers, non-aromatic unsaturated mono- or dicarboxylic ester monomers, monomers based on the half ester of unsaturated dicarboxylic acid monomers, unsaturated mono- or dicarboxylic acid monomers, nitrogen-containing monomer, a nitrile-containing monomer containing amine monomers, cyclic or acyclic, branched or unbranched alkyl vinyl ester monomer, or of the wine container of wine container alkyl acrylate monomers, halogenated or non-halogenated aryl acrylate monomers, carboxylic acid vinyl esters, acetic acid alkenyl esters, carboxylic acid alkenyl esters, vinyl halides, vinylidene halides (vinyl idenehalide) , or any combination thereof, any of which having up to 20 carbon atoms. 在这个方面中,申请人的目的是在适合的单体中公开丙烯酸酯和甲基丙烯酸酯中的任一部分时同时包括丙烯酸 In this aspect, Applicants intend to include both acrylic monomer when appropriate disclosed acrylates and methacrylates any portion of

酯和甲基丙烯酸酯部分。 Acrylate and methacrylate moieties. 因此,将丙烯酸酯单体作为适合的烯属不饱和的第一单体的公开还包括相应的甲基丙烯酸酯单体也是适合的第一单体的公开。 Accordingly, the acrylate monomer is suitable as ethylenically unsaturated first monomer is disclosed further comprising a respective methacrylate monomers are also suitable first monomer is disclosed. 缩写(甲基)丙烯酸酯可以用于表示这种公开。 Abbreviation (meth) acrylate may be used to represent such a disclosure.

在制备本发明的生物活性胶乳时可以使用许多不同的烯属不饱和的第一单体。 In preparing biologically active latex of the present invention can use many different ethylenically unsaturated first monomer. 在一个方面中,烯属不饱和的第一单体的适合的实例包 In one aspect, suitable examples of ethylenically unsaturated first monomer packet

括但不限于苯乙烯、对甲基苯乙烯、氯代甲基苯乙烯、乙烯基甲苯、乙烯、丁二烯、(甲基)丙烯酸甲基酯、(甲基)丙烯酸乙基酯、(甲基) 丙烯酸丙基酯、(甲基)丙烯酸丁基酯、(甲基)丙烯酸戊基酯、(甲基) 丙烯酸缩水甘油基酯、(曱基)丙烯酸异癸基酯、(甲基)丙烯酸月桂基 Including but not limited to, styrene, p-methyl styrene, chloromethyl styrene, vinyl toluene, ethylene, butadiene, (meth) acrylate, (meth) acrylate, (meth yl) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, glycidyl methacrylate, (Yue-yl) acrylate, decyl (meth) acrylate, lauryl

酯、马来酸单甲酯、衣康酸、(甲基)丙烯腈、(甲基)丙烯酰胺、N-羟甲基(甲基)丙烯酰胺、N-(异丁氧基曱基)(甲基)丙烯酰胺、新癸酸乙烯基酯、叔羧酸乙烯基酯、乙酸乙烯基酯、C3-Cs烷基乙烯基醚、c3-c8 Ester, monomethyl maleate, itaconic acid, (meth) acrylonitrile, (meth) acrylamide, N- methylol (meth) acrylamide, N- (isobutoxy Yue-yl) ( meth) acrylamide, vinyl neodecanoate, vinyl esters of versatic acid, vinyl acetate, C3-Cs alkyl vinyl ether, c3-c8

烷氧基乙烯基醚、乙烯基氯、偏二氟乙烯、乙烯基氟、l,l-二氟乙烯、 Alkoxy vinyl ethers, vinyl chloride, vinylidene fluoride, vinyl fluoride, l, l- vinylidene fluoride,

三氟乙烯、四氟乙烯、三氟氯乙烯、六氟丙烯、三氟氯乙烯、全氟丁 Trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluoro butyl

基乙烯、全氟化的C3-C8 oc-烯烃、氟化的C3-Cs烷基乙烯基醚、全氟化的C广C8烷基乙烯基醚、全氟化的C广Cs烷氧基乙烯基醚、等等,或其任何组合。 Group ethylene, perfluorinated C3-C8 oc- olefin, a fluorinated C3-Cs alkyl vinyl ether, perfluorinated C wide C8 alkyl vinyl ether, perfluorinated alkoxy vinyl Cs wide C ether, etc., or any combination thereof. 因此,适合的烯属不饱和的第一单体的卣化类似物也被包括在这种公开中,并且申请人的目的是公开这些单体的任何和所有适合的卣素取代的类似物或衍生物,包括氟取代的类似物、氯取代的类似物、溴取代的类似物、和碘取代的类似物。 Thus, suitable ethylenically unsaturated first monomer wine container analogs are also included in this disclosure, and an object of the Applicant is to any and all suitable prime wine container disclosed substituted analogs of these monomers, or derivatives, including fluorine-substituted analogs, chlorine-substituted analogs, bromine-substituted analogs, and iodine-substituted analogs. 术语"卣素取代的,, 是指包括部分卣素取代的和全卣素取代的,其中任何卣素取代基可以是相同的或者可以是不同的。同样在这个方面中,申请人的目的是当在适合的单体中公开丙烯酸酯和甲基丙烯酸酯的任一部分时包括丙烯酸酯和甲基丙烯酸酯部分都公开。 The term "substituted prime wine container ,, is meant to include substituted and part of the wine container full prime prime substituted wine container, wherein any substituents wine container element may be the same or may be different. Also in this aspect, Applicants intend when suitable acrylate monomers disclosed in any part of acrylate and methacrylate esters include acrylate and methacrylate moieties are disclosed.

在另一个方面中,烯属不饱和的第一单体可以是卣化的或者可以是非闺化的。 In another aspect, the first ethylenically unsaturated monomer may be of the wine container or may be of a non-Gui. 同样地,烯属不饱和的第一单体可以是氟化的或者可以是非氟化的。 Similarly, the ethylenically unsaturated first monomer can be fluorinated or non-fluorinated. 例如,可以使用烷基丙烯酸酯或甲基丙烯酸酯的氟化类似物,以及非氟化的化合物。 For example, alkyl acrylates or methacrylates of fluorinated analogs, and a non-fluorinated compound. 烯属不饱和的第一单体还可以是氯化的或者可以是非氯化的。 Ethylenically unsaturated first monomer can also be chlorinated or can be non-chlorinated. 烯属不饱和的第一单体还可以是溴化的或者可以是非溴化的。 Ethylenically unsaturated first monomer can also be brominated or can be non-brominated. 烯属不饱和的第一单体还可以是碘化的或者可以是非碘化的。 Ethylenically unsaturated first monomer can also be iodinated or can be non-iodinated. 例如,可以使用烷基丙烯酸酯或烷基曱基丙烯酸酯的氟化类似物,以及非氟化的化合物。 For example, an alkyl acrylate or an alkyl acrylate Yue fluorinated analogs, as well as non-fluorinated compounds may be used.

在本发明的又一个方面中,本文中提供的胶乳可以包括基于总的单体重量为约20重量%到约99. 5重量%的烯属不饱和的第一单体。 In yet another aspect of the present invention, the latex provided herein may include unsaturated first monomer is from about 99.5% to about 20% by weight based on the total weight of the alkenyl monomer weight. 在这个方面中,本发明的胶乳还可以包括基于总的单体重量为约30-约99重量%、约40-约97重量%、约50-约95重量%、约60-约90重量%、 或约70-约90重量%的烯属不饱和的第一单体。 In this aspect, the latex of the present invention may further comprise, based on total monomer weight of about 30 to about 99 wt%, from about 40 to about 97 wt%, from about 50 to about 95 wt%, from about 60 to about 90 wt% , or from about 70 to about 90 wt% of an ethylenically unsaturated first monomer. 在这个方面中,申请人的目的是单独地公开这种范围可以合理地包括的每个数值,以及其中包括的任何子区间和子区间的组合。 In this aspect, Applicants' intent is to disclose individually each value of this range may reasonably encompass, as well as any sub-range comprised therein, and a combination of subintervals. 在这个方面,如本领域技术人员理解的,具体的单体的特定的化学及物理特性与最适合于该单体的重量百分数范围有关。 In this respect, as one skilled in the art will appreciate, the specific chemical and physical properties of the particular monomer and the most suitable for the weight percentage of the monomer relating to.

烯属不饱和的阳离子型第二单体 Ethylenically unsaturated cationic monomers second

在另一个方面中,本发明的胶乳聚合物还包括至少一种烯属不饱和的第二单体的聚合产物,所述第二单体是阳离子型的或者是阳离子 In another aspect, the latex polymer of the present invention further comprises a polymerization product of at least one ethylenically unsaturated second monomer, the second monomer is cationic or cation

的前体。 Precursors. 如本文中提供的,为阳离子型的或者是阳离子前体的至少一种烯属不饱和的第二单体可以统称为"阳离子型单体,,,也就是具有正电荷或者可以产生正电荷的任何单体。在一个方面中,这种正电荷可以通过单体中的杂原子(例如,氮)的存在来产生,所述杂原子可以构成连接赋予单体以正电荷的质子或任何其它阳离子型路易斯酸的位置。例如,可以使用季胺单体作为本发明的胶乳中的"阳离子型单体", 其包括通过例如使用酸进行质子化或使用烷基卣化物进行烷基化从本文中公开的任何中性的胺单体得到的季胺单体。示例性的杂原子包括但不限于氮、硫、磷等。因此,阳离子型单体典型地借助其乙烯不饱和的特点并入到胶乳聚合物中。 As provided herein, of at least one ethylenically unsaturated second monomer can be collectively referred to as "cationic monomer ,,, i.e. it has a positive charge or may generate cationic or cation precursor positive charge any monomer. in one aspect, this positive charge may be present in the monomer heteroatoms (e.g., nitrogen) to produce said heteroatoms may be formed of a positively charged proton or any other cationic monomers to impart connector positional Lewis acid, for example, quaternary amine monomers can be used as a latex of the present invention, "cationic monomer", which includes, for example, by protonation using an acid or an alkyl wine container from alkylated compound described herein any neutral disclosed quaternary amine monomers obtained amine monomers. exemplary heteroatoms include but are not limited to, nitrogen, sulfur, phosphorus, and the like. Thus, typically by means of cationic monomer having an ethylene unsaturated features incorporated latex polymer.

适合的阳离子型单体的实例可以至少在属于Krishnan的美国专利申请公布2005/0065284和2005/0003163中找到。 Examples of suitable cationic monomers can be found in US patent application published at least part of Krishnan 2005/0065284 and 2005/0003163 found. 在这个方面中, 阳离子型单体的实例包括但不限于胺单体、酰胺单体、季胺单体、磷铕单体、锍单体、或其任何组合,其任一种都具有最多2Q个碳原子。 In this aspect, examples of cationic monomers include, but are not limited to, an amine monomer, an amide monomer, a quaternary amine monomer, europium phosphate monomer, a sulfonium monomer, or any combination thereof, any of which having up to 2Q carbon atoms. 另外,可以用于本发明的胶乳中的烯属不饱和的阳离子型单体的适合的实例包括但不限于丙烯酸二甲基氨基乙基酯;丙烯酸二乙基氨基乙基酯;甲基丙烯酸二甲基氨基乙基酯;曱基丙烯酸二乙基氨基乙基酯; 曱基丙烯酸叔丁基氨基乙基酯;《i^二曱基丙烯酰胺;《W-二甲基氨基丙基丙烯酰胺;丙烯酰基吗啉;W-异丙基丙烯酰胺;乂W-二乙基丙烯酰胺;二曱基氨基乙基乙烯基醚;2-曱基-1-乙烯基咪唑;凤#-二甲基-氨基丙基甲基丙烯酰胺;乙烯基吡啶;乙烯基节基胺;甲基氯化物季铵化的二甲基氨基乙基丙烯酸酯;曱基氯化物季铵化的二曱基氨基乙基曱基丙烯酸酯;二烯丙基二曱基氯化铵;甲基氯化物季铵化的N,N-二曱基氨基丙基丙烯酰胺;三甲基-(乙烯基氧基乙基)氯化铵;1-乙烯基-2, 3-二曱基咪唑错氯化物;乙烯基爷基胺盐酸盐;乙烯基吡啶 Further, the latex can be used in the present invention, suitable examples of ethylenically unsaturated cationic monomers include, but are not limited to acrylate, dimethylaminoethyl methacrylate; diethylaminoethyl acrylate; methacrylic two dimethylaminoethyl acrylate; Yue diethylaminoethyl methacrylic acid ester; Yue-yl methacrylate, tert-butylaminoethyl acrylate; "i ^ two Yue acrylamide;" W- dimethylaminopropyl acrylamide; acryloyl morpholine; W- isopropyl acrylamide; qe W- diethyl acrylamide; Yue two groups aminoethyl vinyl ether; 2- Yue-1-vinylimidazole; Feng # - dimethyl - aminopropyl methacrylamide; vinyl pyridine; vinyl section ylamine; methyl-chloride quaternized dimethylaminoethyl acrylate; Yue chloride quaternized di aminoethyl group Yue Yue acrylate; Yue diallyl ammonium chloride; the methyl chloride quaternized N, N- two Yue amidopropyl acrylamide; trimethyl - (vinyloxyethyl) chloride ammonium; 1-vinyl -2-imidazol-3-yl Yue wrong chloride; vinyl Lord ylamine hydrochloride; vinyl pyridine

盐酸盐;或其任何组合。 Hydrochloride; or any combination thereof. 尽管这些列举的实例包括游离碱化合物、 和各种季盐例如盐酸盐或甲基氯化物季盐,但是可以赋予单体以正电荷的任何适合的路易斯酸都可以用于形成这一公开的阳离子型单体。 Although these exemplified compounds include the free base, and various quaternary salts such as hydrochloride or methyl chloride quaternary salt, it can impart a positive charge to the monomer Any suitable Lewis acid may be used to form the disclosed cationic monomers.

在另外的方面中,还可以使用其它胺或胺盐作为烯属不饱和的第二单体来制备本发明的胶乳聚合物。 In a further aspect, it may also be used as ethylenically unsaturated second monomers to prepare the latex polymers of the present invention using other amine or amine salt. 例如,可以通过例如使环氧基团 For example, for example by epoxy groups

与仲胺反应并且随后用酸中和新形式的叔胺来得到各种胺盐。 And subsequently reacted with a secondary amine with an acid and a tertiary amine to obtain new forms of various amine salts. 例如, 可以进行甲基丙烯酸缩水甘油基酯与仲胺的反应并将产物自由基聚合。 For example, methylation glycidyl methacrylate with a secondary amine and the reaction product of free radical polymerization. 季胺官能度还可以对具有例如环氧基团的预聚物进行"反应后(post-reaction),,来生成。这种反应的实例描述在论文"Polymer Compositions for Ca"onic Electrodepositable Coatings,,, Journal of Coatings Technology, Vol 54, No 686, March 1982中, 所述论文被全文并入本文作为参考。还应该理解的是,阳离子官能度还可以使用锍或磷错化学来得到,其实例在参考文献中有所描述,如本领域技术人员理解的。 Quaternary amine functionality may also be a prepolymer, for example, be an epoxy group-having "reaction (post-reaction) ,, generates Examples of such reactions are described in the article" onic Electrodepositable Coatings Polymer Compositions for Ca ",, , Journal of Coatings Technology, Vol 54, No 686, March 1982, the papers are incorporated herein by reference. it should also be appreciated that cationic functionality can also be used sulfonium or phosphonium chemistry to obtain error, examples of which references are described, as appreciated by those skilled in the art.

在另一个方面中,本发明的胶乳聚合物可以包括基于总的单体重量为约0. 01-约75重量%的烯属不饱和的第二单体,所述第二单体为阳离子型的或者是阳离子的前体。 In another aspect, the latex polymer of the present invention may comprise based on the total monomer weight unsaturated second monomer is from about 0.5 to about 01- 75 wt% of hexene, the second monomer is a cationic or is a precursor cations. 在这个方面中,本发明的胶乳还可以包括基于总的单体重量为约0. 025-约70重量°/。 In this aspect, the latex of the present invention may further comprise, based on total monomer weight of about 025 to about 0. 70 wt ° /. 、约0. 05-约60重量%、约0. 1-约50重量%、约0. 25-约40重量%、约0. 5-约30重量%、 约1-约20重量%、或者约1. 5-约15重量°/。 , From about 0.5 to about 05- 60 wt%, from about 0. 1 to about 50 wt%, from about 0. 25 to about 40 wt%, from about 0. 5 to about 30 wt%, from about 1 to about 20 wt%, or from about 1. 5 to about 15 wt ° /. 的阳离子型的第二单体。 A second cationic monomer. 在这个方面中,申请人的目的是单独地公开这种范围可以合理地包括的每个数值,以及其中包括的任何子区间和子区间的组合。 In this aspect, Applicants' intent is to disclose individually each value of this range may reasonably encompass, as well as any sub-range comprised therein, and a combination of subintervals. 空间体积大的组分 Space bulky components

如本文中公开的,本发明的一个方面包括阳离子型聚合物胶乳, As disclosed herein, one aspect of the present invention comprises a cationic polymer latex,

其包括:a)本文中公开的胶乳聚合物;b)被至少部分地包封在胶乳聚合物内的至少一种生物活性组分;和c)任选的被并入到胶乳聚合物中的至少一种空间体积大的组分。 Which comprises: a latex polymer a) disclosed herein; b) is at least partially encapsulated within the latex polymer is at least one bioactive component; and c) is optionally incorporated into the latex polymer at least one component of a large volume of space. 被并入到胶乳聚合物中的至少一种空间体积大的组分可以独立地选自至少一种空间体积大的烯属不饱和的 Is incorporated into the latex polymer of at least one sterically bulky component can be independently selected from at least one sterically bulky ethylenically unsaturated

第三单体、至少一种空间体积大的聚合物、或其任何组合。 The third monomer, at least one large space volume of the polymer, or any combination thereof. 在这个方面中,并且尽管不希望束縛于理论,这种空间体积大的组分典型地被并入到阳离子型聚合物胶乳中用以空间上稳定胶乳。 In this aspect, and while not wishing to be bound by theory, this sterically bulky component is typically incorporated into the cationic polymer latex to sterically stabilize the latex.

如本文中使用的,在对于使用至少一种空间体积大的烯属不饱和的第三单体时,术语"并入"包括但不限于将这种第三单体连接于阳离子型聚合物,例如通过使第三单体与本文中公开的第一单体和第二阳离子型单体共聚,以便形成阳离子型聚合物胶乳。 As used herein, when using at least one sterically bulky ethylenically unsaturated third monomer, the term "incorporated" includes, but is not limited to such third monomers are linked to a cationic polymer, for example, by the first monomer and the third monomer disclosed herein, and a second cationic monomer to form the cationic polymer latex. 另外,关于至少一种空间体积大的烯属不饱和的第三单体的术语"并入"还可以包括以任何其它方式将这种第三单体连接于阳离子型聚合物,诸如例如通过接枝在聚合物骨架上。 Further, on at least one sterically bulky ethylenically unsaturated third monomer terms of "incorporated" may also include any other way is connected to a third monomer such cationic polymers, such as for example by contact branches on the polymer backbone. 在另一个方面中,关于使用至少一种空间体积大的聚合物的术语"并入"包括但不限于将这种聚合物连接到或结合在胶乳中,其方法包括但不限于将空间体积大的聚合物吸附或接枝在胶乳表面上。 In another aspect, the terms on the use of at least one sterically bulky polymer "incorporated" includes, but is not limited to be connected to or incorporated in this polymer latex, the method including but not limited to large volume of space a polymer adsorbed or grafted onto the latex surface. 例如,可以用这样的方式将聚乙烯醇并入到胶乳中。 For example, such a manner may be incorporated into the polyvinyl alcohol latex. 这种空间上稳定组分可以包括非离子型单体或非离子型聚合物,其为胶乳粒子引入立体稳定化而不影响阳离子型聚合物胶乳的沉积特征。 Such a stabilizing component may include spatial non-ionic monomer or nonionic polymer which is introduced into the three-dimensional stabilized latex particles without affecting the deposition characteristics of the cationic polymer latex.

可以用作空间体积大的烯属不饱和的第三单体的示例性单体包括的不在于包含烷氧基化(例如,乙氧基化或丙氧基化)官能度的那些烯属不饱和的单体。 Space may be used as bulky ethylenically unsaturated third monomers Exemplary monomers include lies not contain alkoxylated (e.g., ethoxylated or propoxylated) alkenyl functionality that is not the case unsaturated monomers. 在一个方面中,这种单体的实例包括但不限于至少一种独立地选自以下物质的空间体积大的烯属不饱和的化合物: In one aspect, examples of such monomers include, but are not limited to, at least one substance is independently selected from the space unsaturated olefinic compounds bulky:

a)CH2=C(R1A)COO(CH2CHR2A0)J3A,其中R"、 R2A、和R3A可以独立地选自H或具有1-6个(含端值)碳原子的烷基基团,和m可以是l-30 的整数(含端值)。在这个方面中,R1A、 R2A、和R3A还可以独立地选自H或甲基,m可以是1-10的整数(含端值);b) CH2=C(R1B)COO(CH2CH20)n(CH2CHR2B0)pR3B,其中R1B、 R2B、和R3B可以独立地选自H或具有1-6个(含端值)碳原子的烷基基团,并且n和p可以是独立地选自1-15(含端值)的整数。还是在这个方面中,R1B、 R2B、和R38可以独立地选自H或甲基,并且n和p可以是独立地选自l-10(含端值)的整数; a) CH2 = C (R1A) COO (CH2CHR2A0) J3A, wherein R ", R2A, and R3A can be independently selected from H or has from 1 to 6 (inclusive) carbon atoms in the alkyl group, and m may a is an integer from l-30 (inclusive) in this aspect, R1A, R2A, and R3A can also be independently selected from H or methyl, m can be an integer from 1 to 10 (inclusive);. b) CH2 = C (R1B) COO (CH2CH20) n (CH2CHR2B0) pR3B, wherein R1B, R2B, and R3B can be selected independently H or 1 to 6 (inclusive) carbon atoms in the alkyl group, and n and p may be independently selected from 1-15 (inclusive) is an integer. also in this aspect, R1B, R2B, and R38 may be independently selected from H or methyl, and n and p may be independently selected from from l-10 (inclusive) is an integer;

c) CH2=C(Rlc)COO(CH2CHR2C0)q(CH2CH20)rR3C,其中R1C、 R2C、和R3C可以独立地选自H或具有1-6个(含端值)碳原子的烷基基团,并且q和r可以是独立地选自l-15(含端值)的整数。 c) CH2 = C (Rlc) COO (CH2CHR2C0) q (CH2CH20) rR3C, wherein R1C, R2C, and R3C may be independently selected from H or from 1 to 6 (inclusive) carbon atoms in the alkyl group, and q and r can be integers selected independently from l-15 (inclusive) of. 仍在这个方面中,Rie、 R2e、 和R3e可以独立地选自H或曱基,并且q和r可以是独立地选自1-10(含端值)的整数;或者 In this aspect still, Rie, R2e, R3e and may be independently selected from H or Yue group, and q and r may be independently selected from 1-10 (inclusive) is an integer; or

d) 任何这些化合物的任何组合。 d) any combination of any of these compounds.

在本发明的另一个方面中,可以用作空间体积大的烯属不饱和的 In another aspect of the present invention may be used as a large volume of space ethylenically unsaturated

活性剂。 Active agent. 因此,适合的空间体积大的烯属不饱和的第三单体的另外的实例包括但不限于烷氧基化的二羧酸单酯;烷氧基化的二羧酸的二酯; 聚氧乙烯烷基苯基醚例如NOIGEN RNTM;或其任何组合。 Further examples therefore, a large volume of space of suitable ethylenically unsaturated third monomers include, but are not limited to, alkoxylated monoesters of a dicarboxylic acid; alkoxylated diesters of dicarboxylic acids; polyoxyethylene alkylphenyl ether e.g. NOIGEN RNTM; or any combination thereof. 在这个方面中,例如,还可以使用二酸例如马来酸和衣康酸(itaconic acid)的乙氧基化的单酯和二酯来实现期望的稳定作用。 In this aspect, for example, may be used, for example, maleic acid and itaconic acid (itaconic acid) ethoxylated mono and diesters to achieve the desired stabilization. 被称为可聚合表面活性剂的丙烯酸酯、甲基丙烯酸酯、乙烯基和烯丙基类似物又可以以这种方式使用。 It is referred to as polymerizable surfactants acrylate, methacrylate, vinyl and allyl and the like can be used in this manner. 这种可聚合表面活性剂的实例包括但不限于由Cognis出售的TREMLF-40TM。 Examples of such polymerizable surfactants include, but are not limited to, marketed by Cognis, TREMLF-40TM. 在一个方面中,这些表面活性剂在它们具有乙烯不饱和的方面是典型的,这允许表面活性剂被并入到胶乳聚合物本身中, 以及具有不同的疏水性和亲水性官能度。 In one aspect, the surfactant has an unsaturated ethylene aspects thereof are typical, which allows the surface active agent is incorporated into the latex polymer itself, as well as having different hydrophobic and hydrophilic functionalities. 在另一个方面中,特别适用于本发明的表面活性剂包括非离子型表面活性剂,其中亲水性特征被认为可归因于氧化烯基团的存在。 In another aspect, the surfactant is particularly suitable for the present invention include non-ionic surfactants, wherein the hydrophilic character is believed to be attributable to the presence of alkylene oxide groups. 适合的非离子型表面活性剂的实例包括但不限于氧化乙烯、氧化丙烯、氧化丁烯等。 Examples of suitable nonionic surfactants include, but are not limited to, ethylene oxide, propylene oxide, butylene and the like. 在这种物质中,可以基于官能度的选择改变亲水性的程度。 In such a material, it may be changed based on the selected functionality degree of hydrophilicity.

被并入到胶乳聚合物中的至少一种空间体积大的组分还可以构成至少一种聚合物。 Is incorporated into the latex polymer of at least one sterically bulky component can also constitute at least one polymer. 同样,不打算束縳于理论,认为这种聚合物为得到的胶乳聚合物提供空间稳定性。 Similarly, not intending to be bound by theory, that such polymers provide steric stability to the resulting latex polymer. 这种聚合物有时在本领域中被称为保护性胶体。 Such polymers are sometimes referred to as protective colloids in the present art. 空间体积大的聚合物的实例包括但不限于聚乙烯醇、聚乙烯吡咯烷酮、幾基乙基纤维素等,包括这些材料的任何组合。 Large volume of space Examples of polymers include but are not limited to, polyvinyl alcohol, polyvinyl pyrrolidone, ethyl cellulose, a few, including any combination of these materials. 此外, 还可以使用任何上述的空间体积大的单体和任何这些空间体积大的聚合物的混合物或组合作为被并入到胶乳聚合物中的至少一种空间体积大的组分。 In addition, any of the above may also be used sterically bulky monomers and any of these large spatial volume mixture or combination of a large volume of polymer as at least one spatial component is incorporated into the latex polymer. 可以赋予稳定性的可用于本发明中的许多其它单体和聚合 It may impart stability and can be used for many other polymerizable monomers in the present invention

物在Krishnan等人的美国专利5, 830, 934中提供,所述专利被全文并入本文作为参考。 Was 830, 934 are provided in U.S. Patent No. 5 Krishnan et al., Said patent being incorporated herein by reference.

任选的至少一种空间体积大的组分可以以基于总的单体重量为0-约25重量%的量存在。 Optionally at least one sterically bulky component can be based on the total weight of the monomers in an amount of 0 to about 25% by weight. 在这个方面中,本发明的胶乳还可以包括基于总的单体重量为约0. 1-约20重量%、约0. 2-约18重量%、约0. 5-约15重量%、约0. 7-约12重量%、或约1-约10重量%的空间体积大的组分。 In this aspect, the latex of the present invention may further comprise, based on total monomer weight of about 0. 1 to about 20 wt%, from about 0. 2 to about 18 wt%, from about 0. 5 to about 15 wt%, about 0. 7- large component of about 12% by weight, or from about 1 to about 10 wt% of the volume of space. 在这个方面中,申请人的目的是单独地/>开这种范围可以合理地包括的每个数值,以及其中包括的任何子区间和子区间的组合。 In this aspect, Applicants intend each value individually /> On such a range could reasonably be included, as well as any sub-range comprised therein, and a combination of subintervals.

自由基引发剂 Radical initiator

在另一个方面中,本发明的胶乳可以包括自由基引发剂,其选择是本领域技术人员已知的。 In another aspect, the latex of the present invention may comprise a radical initiator, the selection is known to the skilled person. 因此,尽管可以使用任何聚合引发剂作为 Thus, although any may be used as a polymerization initiator

聚合引发剂,无论其性质上属于阳离子型或是阴离子型,例如过硫酸盐、过氧化物等,但是典型的引发剂是基于偶氮基的化合物和组合物。 The polymerization initiator, either cationic or anionic part of its properties, for example persulfates, peroxides, etc., but the initiators are typically azo-based compounds and compositions. 此外,在这个方面中,生产阳离子型胶乳,可以利用在分解时生成阳离子性物质并且有助于胶乳的阳离子电荷的任何自由基引发剂。 Further, in this aspect, the cationic latex produced may be utilized to generate a cationic species upon decomposition and contributes to the cationic charge of the latex of any free radical initiator. 这种引发剂的实例包括但不限于2,2'-偶氮双(2-脒基丙烷)二盐酸盐), 其由WOKO Chemicals of Richmond, Virginia作为WOKO V—50TM4g 售。 Examples of such initiators include, but are not limited to, 2,2'-azobis (2-amidinopropane) dihydrochloride), which is of Richmond, Virginia as sold by the WOKO Chemicals WOKO V-50TM4g.

生物活性剂/抗微生物剂及其并入 The bioactive agent / antimicrobial agent incorporated and

本文中公开的阳离子型胶乳聚合和包封方法可以使用各种抗微生物剂。 Cationic latex polymerization and encapsulation method disclosed herein can use a variety of antimicrobial agents. 阳离子型胶乳已经被证明是非常有用的,这部分地是由于可以用至少一种抗微生物剂加以补充的阳离子型聚合物的固有的抗微生物属性。 Cationic latex has proved very useful, in part to the inherent antimicrobial attributes to be added due to the cationic polymers may be at least one antimicrobial agent. 在这个方面中,本发明还提供用于制备抗真菌剂加强的阳离子型胶乳的方法和用于通过湿部工艺将这种胶乳沉积在纸浆纤维上的方法,使得得到的纸片实质上是抗真菌的。 In this aspect, the present invention also provides a method for preparing the cationic latex antifungal agent and a method for reinforcing portion by a wet process such latex was deposited on pulp fibers, such that the resulting sheet is substantially anti fungi. 包括沉积在纸浆纤维上在内的这种方法强调了将抗微生物活性成分并入到得到的用于沉积的阳离子型胶乳中的这种工艺的应用,部分是因为该工艺由纸浆纤维和阳离子型胶乳上的相反电荷而变得方便。 Comprising pulp fibers is deposited on the inner This method emphasizes the antimicrobial active ingredient is incorporated into the application to obtain the cationic latex for deposition in this process, in part because the process of pulp fibers and cationic opposite charges on the latex becomes easy. 这种相反的电荷特征典型地引起阳离子型胶乳在纤维上的沉积的显著均匀性和产生实质上均质的产物。 This opposite charge features typically causes significant product was generated and uniform deposition of the cationic latex on the fibers is substantially homogeneous. 在这个方面中,典型的引发剂还包括基于偶氮基的化合物和组合物。 In this aspect, the typical initiators also include azo-based compounds and compositions.

如本文中提供的,可以使用各种聚合条件。 As provided herein, various polymerization conditions. 在一个方面中,生物活性组分或添加剂典型地可溶解于所用的至少一种单体中,和/或可溶解于所用的单体混合物或组合物中。 In one aspect, the bioactive component or additive is typically soluble in at least one of the monomers used, and / or a monomer mixture or composition used in soluble in. 在另一个方面中,可以在聚合工艺过程中的任何阶段引入生物活性填加剂,包括在种子形成阶段过程中的非常早的阶段,包括在引发时包括至少一种生物活性组分在内的组合物的所有的组分都存在时引发乳液聚合。 In another aspect, it may be introduced at any stage during the polymerization process biologically active filling additives, including a very early stage during the stage in seed formation, comprising at least one biologically active component comprises at the inner initiated when all of the emulsion polymerization initiator components of the composition are present. 在另一个方面中,生物 In another aspect, the biological

添加剂可以在聚合工艺的随后阶段中加入。 Additives may be added at a later stage of the polymerization process. 例如,可以在约30%的单体已经进料到聚合反应器中时将生物活性成分引入到单体原料中。 For example, polymerization may already fed at about 30% of the monomers in the reactor is introduced into the biologically active ingredient in the monomer feed.

尽管不打算束縳于理论,但是认为在聚合过程的相对晚的时间将生物活性组分引入到单体原料中可以有助于使由于聚合条件所致的生物活性剂降解降低到最低程度。 While not intending to be bound by theory, it is believed that the relatively late time of the polymerization process be introduced into the monomer feed bioactive component can contribute to the biologically active agent since the polymerization conditions due to minimize the degradation. 例如,有可能的是,生物活性剂可能在进行聚合的温度降解,或者可能与某些单体或其它組分反应。 For example, it is possible that the bioactive agent may degrade during the polymerization temperature, or may be monomers or with certain other components of the reaction. 因此, 为了使任何这种降解过程缩到最低程度,可以在工艺中的如下时间加入生物活性剂,例如在工艺的超过约50%、超过约60%、超过约70%、 超过约80%、或超过约90%完成时接加入,从而使生物活性剂和其它组分在聚合条件下的接触时间最小化。 Accordingly, in order to make any such degradation process reduced to a minimum, may be added in the process of time as the bioactive agent, for example, in the process than about 50%, more than about 60%, greater than about 70%, more than about 80%, or when the connection is added to complete than about 90%, so that the bioactive agent and other components to minimize contact time at polymerization conditions. 使生物活性剂降解缩到最低程度的另一个方法是采用包括"潜在的"生物活性部分的生物活性剂,所述"潜在的"生物活性部分可以通过在乳液聚合之后的适合时间借助热、化学品、光化学或类似的方法来活化。 Biologically active agent is reduced to a minimum degradation Another method is to use a chemical comprises "potential" biologically active agent is a biologically active moiety, the "potential" biologically active portion by means of heat at a suitable time after the emulsion polymerization, products, or similar methods photochemically activated. 在本发明的另一个方面中,可以在乳液聚合工艺过程中的任何阶段引入生物活性填加剂,包括例如使得到的抗微生物胶乳表现出的生 In another aspect of the present invention, the biological activity can be introduced at any stage of filling additives in the emulsion polymerization process, comprising for example an antimicrobial latex obtained exhibits green

物活性相对于通过在乳液聚合约50%完成时加入生物活性组分制备的相同的抗微生物胶乳所表现出的标准生物活性没有显著减少的时间。 Activity was not significantly reduced with respect to time exhibited by the same latex prepared antimicrobial bioactive component added during the emulsion polymerization of about 50% complete biological activity standard.

50%完成时加入生物活性组分制备的从相同生物活性组分合成的并且具有基本上相同浓度的相同胶乳的活性。 Preparation of biologically active components are added to the 50% completion of the synthesis of bioactive components from the same and having substantially the same activity at the same concentration of the latex. 术语"没有显著减少"是指得到的生物活性胶乳的活性相对于这种标准生物活性的任何差异符合 The term "not significantly reduced" is meant that the active phase of the biologically active latex obtained for any difference in the biological activity of the standard compliance

任何一个或一个以上的以下标准:i)测量的得到的生物活性胶乳的活 Any one or more of the following criteria: i) measuring the biological activity of the resulting latex live

性比测量的标准的活性低小于等于约15%; 2)基于任意活性比例,得到的生物活性胶乳的活性具有比标准的数字活性评分低小于等于约35%的数字活性评分;或3)得到的生物活性胶乳的活性水平的凭经验的描述评级比标准的活性评级水平低最多两个描述评级水平。 Of specific activity of the standard measurement of a low of less than equal to about 15%; 2) any active ratio based on active bioactive latex obtained than standard digital active low score less than or equal to about 35% of the figure activity score; or 3) to give empirically level of activity of the biologically active latex described rating rating than the standard level of activity up to two lower level rating is described. 抗微生物活性的测量可以根据以下任何一个或一个以上的试验标准来测定: ASTME2180-01; ASTM E2149-01; ASTM E1882-05; ASTMD3273; AATCC Test Method 30, Part 3; AATCC Test Method 100; ASTM D5590。 Measurement of antimicrobial activity may be determined according to the following test criteria of any one or more of: ASTME2180-01; ASTM E2149-01; ASTM E1882-05; ASTMD3273; AATCC Test Method 30, Part 3; AATCC Test Method 100; ASTM D5590 . "没有显著减少的标准l)的实例如下。"可以在乳液聚合工艺过程中的一个时间引入生物活性填加剂,或者在乳液聚合工艺过程中的一个时间开始引入,以便为得到的抗微生物胶乳提供0. 009 mg/mL的最小抑菌浓度(MIC),其比标准的0. 010mg/mL的MIC低不到15%。 "Did not significantly reduce the standard l) the following Examples." Bioactive filling additives may be incorporated in a time of the emulsion polymerization process, emulsion polymerization process or start the process of introducing a time, to an antimicrobial latex was obtained provided 0. 009 mg / mL of the minimum inhibitory concentration (MIC), which is more than the standard 0. 010mg / mL lower MIC of less than 15%. "没有显著减少"的标准2)的实例如下。 "Not significantly reduced" standard of Example 2) as follows. 可以在乳液聚合工艺过程中的一个时间引入生物活性填加剂,或者可以在乳液聚合工艺过程中的一个时间开始引入,以便为得到的抗微生物胶乳提供基于任意的活性比例为5的数字活性评分,其比标准的7的数字活性评分低不到35%。 Can be introduced during the emulsion polymerization process of filling a biologically active additive of time, or may be a time during the emulsion polymerization process begins introduced, in order to provide any active ratio based on a digital activity score 5 is an antimicrobial latex obtained , which is less than 35% lower than the standard number 7 activity score. "没有显著减少"的标准3)的实例如下。 "Not significantly reduced" standard 3) of the examples are as follows. 在包括"优异的活性"、"非常好的活性"、和"良好的活性"的连续评级水平的基于经验的描述评级系统中,可以在乳液聚合工艺过程中的一个时间引入生物活性填加剂,或者在乳液聚合工艺过程中的一个时间开始引入,以便为得到的抗微生物胶乳提供相对于标准的"优异的活性"的活性评级为"良好的活性"的活性评级。 Experience-based rating system described, the biological activity can be introduced in the filling additives of the emulsion polymerization process includes a time "excellent activity", "very good activity", and "good activity" of successive level rating or a time during the emulsion polymerization process begins introduced to provide a rating relative to the activity of the standard "excellent activity" is obtained as an antimicrobial latex "good activity" activity rating. 在活性的任何这些测量方法中,可以在提供这种结果的聚合过程中的任何时间引入生物活性填加剂,或者可以在提供上述公开的结果的聚合过程中的时间开始引入。 In any of these measurements of activity, biological activity can be introduced during polymerization filling additives provided such a result any time, or may be incorporated during polymerization start providing the above disclosed results in time.

在另一个方面中,不需要在聚合工艺的相对晚的时间将生物活性 In another aspect, the biological activity is not necessary to relatively late times in the polymerization process

组分引入到单体原料中。 Components into the monomer feed. 例如,还可以在已经将约0%、约10%、约20%、 约30%、约40%、约50%、约60%、约70%、约80%、约90%、或约100% 的单体进料到聚合反应器中时加入生物活性添加剂。 For example, also it has been to about 0%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%, or about 100 % of the monomers fed to the polymerization reactor was biologically active additives. 在这个方面中, 组合物的并非所有组分都从开始时就都存在的时候引发乳液聚合,而有一些是在引发聚合之后在不同的时间加入的,包括但不限于至少一种生物活性组分。 In this aspect, not all components of the composition are present from the start time to initiate the emulsion polymerization are, but some are added after the polymerization is initiated at different times, including but not limited to at least one bioactive group Minute. 还在这个方面中,申请人的目的是公开这种数值范围内的任何和所有范围,并且单独地要求保护这种范围可以合理地包括的每个可能的数值,以及其中包括的任何子区间和子区间的组合。 Also in this aspect, Applicant's intent is to any and all ranges disclosed within this numerical range, and claimed individually each possible number that such a range could reasonably encompass, including any sub-section, and wherein sub and combination interval.

在另一个方面中,可以在一个温度范围内进行聚合反应,典型地在提供合理的聚合速率的最低温度和不引起抗微生物的生物活性成分显著降解或分解可允许的最高温度之间进行选择。 In another aspect, the polymerization reaction can be carried out within a temperature range, typically to make selections between the highest temperature of the coldest reasonable polymerization rate and does not cause the antimicrobial active ingredient biologically significant degradation or decomposition can be permitted. 在一个方面中,聚合反应可以在可能进行聚合反应的最低温度进行。 In one aspect, the polymerization reaction may be carried out at the lowest possible temperature of the polymerization reaction. 在这种情况中,聚合反应温度应该充分地低,使得被并入的任何生物活性成分不会显著地降解或分解,但是也足够高,使得聚合速率和时间适用于有效率地生产最终的胶乳聚合物。 In this case, the polymerization temperature should be sufficiently low that any biologically active ingredient is incorporated does not significantly degrade or decompose, but high enough such that polymerization rates and times suitable for the efficient production of the final latex polymer.

料将单:、添加剂:表面活性剂、水等的混合物乳:而制备的预制乳 The single material: milk mixture of surfactants, water and the like::, preformed additive prepared milk

液(pre-emulsion)进料。 Solution (pre-emulsion) feed. 例如,在这个方面中,可以通过使用相对浓缩的量的添加剂并且通过使用表面活性剂、分散剂等分散,并且典型地采用诸如高速搅拌器、勻化器、Eppenbach混合器、或类似装置的混合装置来生产分散体,也可采用其它方法来生产。 For example, in this aspect, by using a relatively concentrated amount of the additive and by the use of surfactants, dispersants, and the like dispersed, and typically employed as a high-speed stirrer, a homogenizer, an Eppenbach mixer, or similar mixing device means for the production of dispersions, other methods may also be produced. 此外,可以利用本领域技术人员已知的任何其它想得到的提供其中添加剂是分散体、 乳液、悬浮液等,或者添加剂在聚合反应之前基本上溶解于单体混合物中的工艺。 Moreover, the use of any other conceivable provided wherein the additive is a dispersion, emulsion, suspension and the like known to the skilled person, or substantially dissolved in the additive process the monomer mixture prior to polymerization.

在一个方面中,在许多情况中,提供抗真菌和抗细菌性能的有用的抗微生物剂可能是对氧化或还原敏感的,尤其是在暴露于较高的温度时。 In one aspect, in many cases, to provide anti-fungal and anti-bacterial properties useful antimicrobial agents may be sensitive to oxidation or reduction, especially when exposed to higher temperatures. 因此,除了抗微生物剂溶解度之外,选择和并入抗微生物剂的另一个方面是使会降解这种组分的任何氧化或还原反应减少。 Thus, in addition to the antimicrobial agent than the solubility, another aspect of selecting and incorporating the antimicrobial agent is to degrade such components any oxidation or reduction reaction reduced. 本发明的工艺可以典型地通过控制聚合反应温度、调节将活性成分加入到反应中的时间段以便控制对聚合反应温度的接触、通过在聚合反应过程中加入适当的氧化剂或还原剂以减少或緩和任何氧化还原降解、或这些方法的任何组合来实现这种结果。 The process of the invention can be typically achieved by controlling the polymerization temperature, adjusting the active ingredient is added to the reaction period in order to control exposure to the polymerization temperature, by adding suitable oxidizing or reducing agent during the polymerization reaction to reduce or mitigate any redox degradation, or any combination of these methods to achieve this result.

在本发明的另一个方面中,至少一种生物活性组分可以独立地选 In another aspect of the present invention, the at least one biologically active component may be independently selected from

自十一碳烯酸;十一碳烯醇;十一碳烯酸与羟基乙基(曱基)丙烯酸酯或聚乙二醇(曱基)丙烯酸酯的反应产物;十一碳烯醇与(甲基)丙烯酸、 马来酐、或衣康酸的反应产物;壳聚糖(chitosan)或改性的壳聚糖; 或其任何组合。 From undecylenic acid; undecylenic alcohol; undecylenic acid and hydroxyethyl (Yue-yl) acrylate or the reaction product of polyethylene glycol acrylate (Yue-yl); and undecenol ( methyl) reaction products of acrylic acid, maleic anhydride, or itaconic acid; chitosan (chitosan) or modified chitosan; or any combination thereof. 可以用于本发明的另外的抗微生物组分提供在Krishnan的美国专利申请公布2005/0003163中,其被全文并入本文作为参考。 The additional antimicrobial component may be used in the present invention are provided in U.S. Patent Application Publication Krishnan 2005/0003163, which is incorporated herein by reference. 本发明的另一个方面提供至少一种生物活性组分,其可以独立地选自铜、铜盐、银、银盐、锌、锌盐、氧化银、氧化锌、氯己定、氯己定葡糖酸盐、戊二醛、哈拉宗、六氯酚、呋喃西林、硝甲酚汞、聚维酮-碘、硫柳汞(thimerosol) 、 C广到C广对羟基苯甲酸酯、 次氯酸盐、clofucarban、氯节酚、泊洛沙姆-硪、酚醛树脂、乙酸磺胺米隆、盐酸氨吖啶、季铵盐、奥昔氯生(oxychlorosene)、美溴沙仑、汞溴红、二溴沙仑、月桂酸甘油酯、吡石克翁盐(pyrithione salt)、 p比硫翁钠(sodium pyrithione) 、 p比疏翁锌(zinc pyrithione)、 (十二烷基)(二亚乙基二胺)甘氨酸、(十二烷基)(氨基丙基)甘氨酸、 苯酚、间曱酚、邻曱酚、对曱酚、邻苯基-苯酚、间苯二酚、乙烯基苯酚、聚合的胍、多粘菌素、杆菌肽、环杆菌素、八肽霉素(octapept ins )、 溶菌酶(lysozmye )、溶葡球菌霉(ly Another aspect of the present invention provides at least one biologically active component, which may be independently selected from copper, copper salts, silver, silver salts, zinc, zinc salts, silver oxide, zinc oxide, chlorhexidine, chlorhexidine glucosidase saccharate, glutaraldehyde, Sahara cases, hexachlorophene, nitrofurazone, nitromersol mercury, povidone - iodine, thimerosal (thimerosol), C to C broad wide parabens, hypochlorite , clofucarban, section chloro phenol, poloxamer - Wo, phenol resins, mafenide acetate, ammonia acridine hydrochloride, quaternary ammonium salts, triclosan oxybutynin (oxychlorosene), United States bromo Sharon, merbromin, dibromo Sharon, glyceryl laurate, onium salts pyrazol-grams (pyrithione salt), p Weng ratio of sulfur to sodium (sodium pyrithione), p-repellent than zinc pyrithione (zinc pyrithione), (dodecyl) (diethylenediamine) glycine, (dodecyl) (aminopropyl) glycine, phenol, m-Yue phenol, o-phenol Yue, Yue of phenol, o-phenyl - phenol, resorcinol, vinyl phenol, polymeric guanidines, polymyxa cephalosporins, bacitracin, bacteriocins ring, octapeptide neomycin (octapept ins), lysozyme (lysozmye), lysostaphin mildew (ly sostaphin )、纤维素酶(cellulytic enzymes)、万古霉素、利托菌素、类放线菌素、阿伏帕星(aroparcins)、短杆菌酪肽A (tyrocidin A)、短杆菌肽S、多氧菌素D (polyoxin D)、衣霉素、新霉素、链霉素、或其任何组合。 sostaphin), cellulase (cellulytic enzymes), vancomycin, ristocetin, class actinomycin, avoparcin (aroparcins), tyrocidine A (tyrocidin A), gramicidin S, multiple polyoxin D (polyoxin D), tunicamycin, neomycin, streptomycin, or any combination thereof. 本发明的又一个方面提供可以表现出杀真菌活性的至少一种生物活性组分。 A further aspect of the present invention may exhibit provides at least one biologically active component of fungicidal activity. 在这个方面中,适用于本发明的适合的杀真菌剂包括但不限于吡咯类、季铵化合物、二硫代氨基甲酸酯类、二曱酰亚胺类、或其任何组合。 In this aspect, suitable fungicides suitable for the present invention include, but are not limited to azoles, quaternary ammonium compounds, dithiocarbamates, two Yue imides, or any combination thereof. 例如,在这个方面中,吡咯杀真菌剂可以选自阿扎康唑、 For example, in this aspect, pyrrole fungicide selected A Zhakang oxazole,

联苯三唑醇(biternatol)、溴克座、环丙唑醇、烯唑醇、腈苯唑、氟珪峻、烯菌灵、抑霉峻、imibenconazole、叶菌哇(Metconazole)、 Biphenyl triadimenol (biternatol), bromo g seat, cyproconazole, diniconazole, fenbuconazole, Gui-fluoro-Jun, alkenyl benomyl, Jun imazalil, imibenconazole, metconazole wow (Metconazole),

多效哇、perfuazoate、戊菌哇、珪氟哇、三哇酮、三哇醇、烯效哇、 或其任何组合。 Pleiotropic wow, perfuazoate, penconazole wow, Gui-fluoro-wow, three wow ketones, alcohols three wow, wow uniconazole, or any combination thereof. 还在这个方面中,二硫代氨基曱酸酯杀真菌剂可以选 Also in this aspect, Yue dithiocarbamate fungicide can be selected from ester

自代森锰锌、代森锰、代森联、代森锌、或其任何组合。 From mancozeb, maneb, metiram, zineb, or any combination thereof.

在另一个方面酯,适合的杀真菌剂可以包括但不限于咯菌睛、氟会喳(fluquinconazole )、苯醚曱环哇、4, 5—二曱基—N—(2-丙烯基)-2-(三甲基甲硅烷基)-3-噻吩曱酰胺(硅噻菌胺,sy 1 thiopham)、 Esters, suitable fungicides can include, but are not limited to, fludioxonil eye in another aspect, the chirp will fluoro (fluquinconazole), ether Yue ring wow, 4, 5-Yue-yl -N- (2- propenyl) - 2- (trimethylsilyl) -3-thiophene carboxamide Yue (silthiofam, sy 1 thiopham),

己峻峻(hexaconazole )、 乙环哇磷(etaconazole )、灭菌哇、粉唾醇、氟环峻、糠菌峻(bromuconazole)、四氟醚峻(tetraconazole )、 腈菌唑、联苯三哇醇、嘧霉胺(Pyremethanil)、嗜菌环胺、十三吗啉、 丁苯p马淋(fenpropimorph ) 、 St菌酉旨(kresoxim—methyl ) 、 p密菌酉旨 Hexyl Jun Jun (hexaconazole), B ring wow phosphorus (etaconazole), sterilization wow, saliva alcohol powder, a fluorine ring Jun, Jun bromuconazole (bromuconazole), tetraconazole Jun (tetraconazole), myclobutanil, biphenyl three wow alcohols, pyrimethanil (Pyremethanil), cyclic amines addicted bacteria, tridemorph, fenpropimorph p Ma leaching (fenpropimorph), St bacteria unitary purpose (kresoxim-methyl), p-tight bacteria unitary purpose

(azoxystrobin) 、 ZEN90160TM、拌种咯、苯霜灵、呋霜灵、曱霜灵 (Azoxystrobin), ZEN90160TM, fenpiclonil, benalaxyl, furalaxyl, oxadixyl Yue

(metalaxyl) 、 R-甲霜灵、曱呋酰胺(ofurace)、喁霜灵、萎锈灵、 咪鲜胺(prochloraz )、氟菌唑、咬斑將(pyr if enox)、苯并(1,2,3) 蓉二唑-7-硫代羧酸-S-甲酯(Acibenzolar-S-methyl)、百菌清 (Metalaxyl), R- metalaxyl, ofurace Yue (ofurace), breathing of fish oxadixyl, carboxin, prochloraz (prochloraz), triflumizole, biting the spot (pyr if enox), benzo (1, 3) two Rong-7-carbothioic acid -S- methyl ester (Acibenzolar-S-methyl), chlorothalonil

(chlorothalonil )、霜脲氰、烯酰吗啉、嚙唑菌酮、苯氧会啉 (Chlorothalonil), cymoxanil, dimethomorph, famoxadone Nie, phenoxy will morpholine

(quinoxyfen )、苯锈咬(f enpropidine)、螺环菌胺(spiroxamine )、 咪唑溱(triazoxide) 、 BAS50001F™、噍霉灵(hymexazol)、戊菌隆、 咪唑菌酮、双胍辛(guazatine)等,包括其任何组合。 (Quinoxyfen), fenpropidin bite (f enpropidine), spiroxamine (spiroxamine), imidazole Qin (triazoxide), BAS50001F ™, Jiao mold Ling (hymexazol), pencycuron, fenamidone, Iminoctadine (Guazatine), etc. , including any combination thereof. 本发明的另一个方面提供适合的杀真菌剂,其可以包括但不限于苯菌灵(又名苯菌灵,benomyl)、 克菌丹、多菌灵(carbendazim) 、 capropamid、 乙嘧酚(ethirimol )、氟酰胺、三乙膦酸铝(fosety卜aluminum)、麦穗宁、hymexanol、春雷霉素、双胍辛胺-三乙酸盐、种菌唑 Another aspect of the present invention to provide a suitable fungicide which may include but are not limited to, benomyl (also known as benomyl, benomyl), captan, carbendazim (carbendazim), capropamid, ethirimol (ethirimol ), flutolanil, fosetyl-aluminum (fosety aluminum Bu), fuberidazole, hymexanol, kasugamycin, iminoctadine - triacetate, ipconazole

(ipconazole )、异菌脲、灭锈胺(mepronil )、曱霜灵-M (mefenoxam)、 氟苯嘧咬醇(nuarimol)、喹啉铜、奮菌酮(oxolinic acid )、稻痘酯(perfurazoate)、盐酸霜霉威、百快隆、五氯硝基苯(又名PCNB)、 硅噻菌胺(silthiopham) 、 MONTM65500、四氯硝基苯、噻菌灵、赛氟灭、甲基硫菌灵(thiophenate-methyl )、福美双(thiram)、甲基立枯磷(tolclofos-mehtyl )、氟菌唑等,包括其任何组合。 (Ipconazole), iprodione, mepronil (mepronil), Yue oxadixyl -M (mefenoxam), bite-fluorophenyl ethyl alcohol (nuarimol), oxine-copper, Fen cycloheximide (oxolinic acid), rice pox ester (perfurazoate ), propamocarb hydrochloride, one hundred long fast, quintozene (also known as PCNB), silthiofam (silthiopham), MONTM65500, tecnazene, thiabendazole, flufenamic race, thiophanate-methyl Ling (thiophenate-methyl), thiram (thiram), tolclofos-methyl (tolclofos-mehtyl), triflumizole like, including any combination thereof. 此外, 可以使用任何这些杀真菌剂的任何组合物或混合物。 Moreover, any combination or mixture of any of these fungicides can be used.

在本发明的又一个方面中,可以在乳液聚合过程中加入的典型的生物活性组分的量可以基于总的单体重量为约0. 01-约40重量%的生物活性填加剂。 In yet another aspect of the present invention, a typical amount of bioactive component may be added during the emulsion polymerization may be from about 0.5 to about 01- 40% by weight of the biologically active additive based on the total fill weight of the monomers. 在另一个方面中,可与在乳液聚合过程中加入的生物活性组分的典型的量可以基于总的单体重量为约0. 025-约35重量%、 约0. 05-约30重量%、约0. l-约25重量%、约0. 25-约20重量%、或约0. 5-约15重量%的生物活性填加剂。 In another aspect, the typical amount added during the emulsion polymerization of bioactive components may be based on the total monomer weight of about 0. 025 to about 35 wt%, from about 0.5 to about 05- 30 wt% , from about 0.5 to about 25 wt% L-, from about 0. 25 to about 20 wt%, or from about 0. 5 to about 15 wt% of the bioactive filler additive. 在这个方面中,申请人的目的是单独地公开这种范围可以合理地包括的每个数值,以及其中包括的任何子区间和子区间的组合。 In this aspect, Applicants' intent is to disclose individually each value of this range may reasonably encompass, as well as any sub-range comprised therein, and a combination of subintervals. 与作为"后加入"添加的抗微生物组分的量相比,生物活性填加剂的这些浓度典型地比时候加入的量大得多。 As compared with the amount of antimicrobial component is added "is added after", the concentration of the bioactive filler is typically much greater than additive when added in an amount. 尤其是,这些特征提供稳定的浓缩分散体,其可以作为浓缩物、作为添加剂使用,或者作为可以被稀释并且加入到需要抗微生物保护的其它系统中的浓缩的分散体使用。 In particular, these features provide a stable concentrated dispersion, as a concentrate which can be used as an additive, or as can be diluted and added to other systems requiring antimicrobial protection in the concentrated dispersions.

如本文中公开的,在一个方面中,典型地在乳液聚合工艺过程中将生物活性组分溶解于单体原料中。 As disclosed herein, in one aspect, the emulsion polymerization will typically be in the process of the bioactive ingredient is dissolved in the monomer feed. 因此,生物活性填加剂典型地至少部分溶解于所用的一种或多种单体中。 Biological activity, thus filling additives typically at least partially dissolved in one or more of the monomers used. 另外,生物活性填加剂可以是中等可溶、显著可溶、或高度可溶于所用的一种或多种单体中。 Further, the bioactive additive can be moderately soluble filler, appreciably soluble, or highly soluble in one or more of the monomers used. 这种特征尤其是可以允许并入疏水性生物活性成分、使用大量和高浓度的生物活性成分、更好地控制抗微生物性能(包括增强抗微生物性能的有效性)、使用最少量的表面活性剂、和生物活性成分的至少部分包封。 This particular feature may allow a biologically active ingredient incorporated into the hydrophobic, bioactive ingredient, and the use of a large number of high concentration, better control of the antimicrobial properties (including enhancing the effectiveness of antimicrobial properties), with a minimum of surface-active agent and at least partially encapsulated bioactive ingredient. 在有些情况下,胶乳聚合物可以充分地包封添加的生物活性组分,因此胶乳聚合物可以作为活性成分的一种类型的载体起作用。 In some cases, the latex polymer can be sufficiently encapsulated bioactive components added, thus the latex polymer can be used as one type of the active ingredient carrier function. 这种工艺还可以并入抗微生物成分而不显著地降解这些化合物的活性。 This process may also incorporate an antimicrobial component without significantly degrading activity of these compounds.

在另一个方面中,在本发明中有用的生物活性添加剂也可以具有任何程度的水溶性,包括显著的水溶性,其实例包括邻苯基苯酚盐(去除质子化的邻苯基苯酚)、和类似的试剂。 In another aspect, the present invention is useful in the biologically active additive may also have any degree of water solubility, including a significant water-soluble, and examples thereof include o-phenylphenol salt (deprotonated o-phenylphenol), and similar reagents. 因此,不需要这种亲水性的生物活性填加剂可溶解于要聚合的任何单体中。 Therefore, no such hydrophilic bioactive filling additives may be dissolved in any of the monomers to be polymerized. 在另一个方面中,本 In another aspect, the present

发明中有用的生物活性添加剂可以实质上不溶解于要聚合的单体中和实质上不溶于水。 Useful in the invention, the biologically active additive may be substantially not dissolved in the monomer to be polymerized and substantially insoluble in water. 在这个方面中,可以通过借助表面活性剂等分散某一浓度的添加剂、典型地使用高速搅拌器或匀化器来制备生物活性组分的分散体,也可以采用其它方法。 In this aspect, the active agent can be dispersed by means of a surface concentration of additives typically dispersions are prepared of bioactive components using a high speed stirrer or homogenizer, other methods may be employed.

因为后加入的添加剂典型地是后混合到制剂中的分散体,其可能难以使生物活性填加剂充分地分散到聚合物膜、粘合剂、涂层等中, 所述生物活性填加剂在其中使用。 Because the addition of additives typically mixed into the dispersion formulation, which may be difficult to fill the biologically active additive is sufficiently dispersed into the polymer film, binder, coating and the like, the bioactive filling additives in which to use. 此外,现在使用的典型的添加剂分散体可以引起水分敏感性和添加剂的浸出或与之相关,并且许多后加 Furthermore, typical additives present dispersions can cause leaching or associated with moisture sensitivity and an additive, and many post-added

入的添加剂不能在产品内持续足够的时间段以提供充分的抗真菌保护。 The additive is not within the product for a sufficient period of time to provide adequate antifungal protection. 本发明提供的方法允许使用最少量的表面活性剂来将生物活性添加剂并入到胶乳中,并且因为生物活性是在聚合反应过程中引入的, 它们典型地被包封起来并且不容易从得到的胶乳中释放出来。 The present invention provides a method allows the use of a minimum amount of surfactant to be incorporated into the biologically active additives to the latex, and because biological activity is introduced during the polymerization process, they are typically encapsulated and are not easily obtained from latex released. 结果是, 生物活性组分的浸出较少,并且生物活性成分在聚合物膜、粘合剂、 涂层等中的总的分布更好。 As a result, less leaching of the biologically active component, and the total distribution of the bioactive ingredient in the polymer film, binder, coating and the like better. 因此,这种方法可以提供可能更安全和更加环境友好的分散体,同时还提供持续的抗真菌或抗细菌保护。 Therefore, this method can provide a potentially safer and more environmentally friendly dispersion, while also providing a continuous anti-fungal or anti-bacterial protection.

本文中公开的工艺还允许胶乳作为浓缩物使用,这与本文中提供的不稳定的那些典型的浓缩物分散体形成对比。 The process disclosed herein also allows the latex used as a concentrate, the typical instability of this concentrate provided herein dispersion contrast. 结果是,典型的浓缩物分散体不能容易地处理并且因此不能容易地被并入到最终产品中, 并且如果剂量增加,则可能对性能(例如水敏感性)产生有害的影响。 As a result, the typical concentrate dispersions can not be easily handled and thus can not be easily incorporated into the final product, and if the dose increases, it may adversely affect the performance (e.g., water sensitivity).

;它材料二起:用或不与其它材料一起使用二如果^要这种材料提; ; From two other materials: ^ if not used two to provide such materials with or together with other materials;

充足的添加剂水平。 Adequate level of additives. 用这样的方式密切并入活性成分可以提供添加剂 In this manner the active ingredients may be provided in close incorporated additives

的均匀分布并且与预先制造的分散体相比产生优异的和持续的性能。 The uniform distribution of the dispersion and resulting in excellent pre-manufactured and sustained performance compared.

生物活性剂的这种密切并入的另外的优点在使用这些胶乳制备的薄膜 An additional advantage of this close bioactive agent incorporated in films prepared using these latex

中是显而易见的,观察到所述薄膜是实质上透明的。 Is apparent, the film was observed to be substantially transparent. 这种特征强调生 This characteristic emphasis on students

物活性剂高度均质地同化在胶乳粒子中以及这种均匀分布如何可以为 Active agent in a highly homogeneous assimilation of the latex particles and how this uniform distribution can be

例如透明的生物活性薄膜等应用提供有用的性能。 For example, transparent film or the like biological activity useful properties applications. 其它添加剂 Other additives

在本发明的另一个方面中,本文中提供的胶乳还可以包括其它添加剂,用以改善聚合物的物理和/或机械性质,其选择为本领域技术人员公知的。 In another aspect of the present invention, the latex provided herein can also include other additives to improve the physical and / or mechanical properties of the polymer, the choice to those skilled in the art. 这种添加剂包括例如工艺助剂和性能助剂,包括但不限于交联剂、天然的或合成的粘合剂、增塑剂、软化器、泡沫抑制剂、泡 Such additives include, for example, process aids and performance aids, including but not limited to, crosslinking agents, natural or synthetic binders, plasticizers, softeners, foam inhibitors, foam

沫助剂、阻燃剂、分散剂、pH调节组分、多价螯合剂或螯合剂、或其它功能性组分、或其任何适合的组合。 Froth aids, flame retardants, dispersing agents, pH adjusting components, sequestering or chelating agents, or other functional components, or any suitable combination thereof.

示例性的基材和生物活性阳离子型聚合物胶乳的应用将本发明的胶乳聚合物涂料沉积在许多不同的基材(例如,纺织品、金属、纤维素材料、塑料等)上可以赋予那些材料以期望的产品使用性能,并且因此为个性化应用定制基材。 Exemplary substrates and bioactive cationic polymer latex The latex applied polymer coating of the present invention is deposited in a number of different substrates (e.g., textiles, metal, cellulosic materials, plastics, etc.) can impart to those materials desired product performance, and therefore apply custom substrates personalized. 例如,在一个方面中,本发明提供一种处理的纤维材料,其可以包括至少一种纤维和至少一种本文中提供的生物活性阳离子型聚合物胶乳。 For example, in one aspect, the present invention provides for processing of fibrous material, which may include a bioactive cationic polymer latex of at least one fiber and at least one provided herein. 在一个方面中,处理的纤维材料可以包括至少一种纤维和布置在至少一种纤维上或与至少一种纤维结合的至少一种生物活性阳离子型聚合物胶乳。 In one aspect, the treated fibrous material can comprise at least one bioactive cationic polymer latex and at least one fiber disposed on at least one fiber or in combination with at least one fiber. 如果期望,可以对纤维应用粉末的形式的生物活性阳离子型聚合物,或者可以通过本领域技术人员已知的任何适合的方法将聚合物组合物沉积在纤维上。 If desired, the bioactive cationic polymer fibers applied in the form of powder, or may be by any suitable method known to those skilled in the polymer composition is deposited on the fibers.

如本文中使用的,术语"纤维,,应该广泛地解释,并且可以包括可以以各种形式存在的单纤维或多重纤维。应该理解,只有单纤维可 As used herein, the term "fiber ,, should be construed broadly, and may include a variety of forms can be present in a single fiber or multiple fibers. It should be appreciated that only a single fiber can be

以用本发明的生物活性阳离子型聚合物胶乳处理,如果需要这样的话。 Latex treated with the bioactive cationic polymer of the present invention, if so desired. 可用于与本发明结合的纤维可以包括天然纤维、合成纤维、或其任何 Fibers may be used in conjunction with the present invention may include natural fibers, synthetic fibers, or any

组合物或混合物。 Composition or mixture. 天然纤维包括但不限于动物纤维类(例如,丝和羊毛);矿物纤维(例如,石棉);和基于植物的纤维(例如,棉、亚麻、 黄麻、和苎麻)。 Natural fibers include, but are not limited to animal fiber (e.g., silk and wool); mineral fibers (e.g., asbestos); and vegetable-based fibers (e.g., cotton, flax, jute, and ramie). 合成纤维包括但不限于由例如聚酰胺、聚酯、丙烯树脂、和聚烯烃的聚合物生产的那些。 Synthetic fibers including, but not limited to those produced by, for example, polyamide, polyester, acrylic resin, and polyolefin polymers. 纤维的其它实例包括但不限于人造丝和以纤维形式挤出的无机物质,例如玻璃、硼、碳化硼、氮化硼、碳、石墨、硅酸铝、熔凝二氧化硅、和金属例如钢。 Other examples of fibers include, but are not limited to rayon and inorganic substances extruded in fibrous form and, for example, glass, boron, boron carbide, boron nitride, carbon, graphite, aluminum silicate, fused silica, and metals such as steel . 在另一个方面中, 纤维素纤维或木纤维也可以用本发明的生物活性阳离子型聚合物胶乳处理,如果期望这样的话。 In another aspect, cellulosic or wood fibers may also be treated with a cationic polymer latex of the present invention, the biological activity, if so desired. 还可以采用使用例如上述材料的任何适合的纤维产生的再生纤维。 It may also be employed using any suitable fibers such as regenerated fibers produced by the above materials. 纤维的任何混合物都可以使用本发明的生物活性阳离子型聚合物胶乳来处理,如果需要这样的话。 Any mixture of fibers can be used by the bioactive cationic polymer latex of the present invention is processed, if so desired.

在另一个方面中,处理的纤维材料具有布置在纤维上的至少一个其它聚合物层,以便形成复合的纤维结构,因此,如果期望,可以使用各种类型的多重聚合物层。 In another aspect, the fibrous material treated with at least one other polymeric layer disposed on the fibers, to form a composite fibrous structure, thus, if desired, can use various types of multi-layer polymer. 例如,可以将阴离子型聚合物胶乳沉积在处理的纤维材料上,用以增强处理过的纤维材料的具体性能。 For example, anionic polymer latices may be deposited on the treated fibrous material to enhance specific properties of the treated fibrous material. 在另一个方面中,可以使用可选的生物活性阳离子型聚合物胶乳和阴离子型聚合物胶乳以连续的方式处理纤维材料,以形成多重层状结构。 In another aspect, you can use the optional bioactive cationic polymer latex and anionic polymer latex in a continuous manner fibrous material to form a multi-layered structure. 尽管不束缚于理论,但是认为阳离子和阴离子聚合物之间的简单的电荷相互作用增强这种结构的稳定性,使得处理过的纤维材料是稳固的。 While not to be bound by theory, it is believed that a simple charge transfer between the interaction of cationic and anionic polymers enhance the stability of this structure, such that the treated fiber material is robust. 可以类似地使用各种其它非生物活性的聚合物的层,例如沉积在存在于纤维材料上的阳离子型聚合物胶乳上,以形成复合结构。 The various layers may similarly be used in other non-biologically active polymers, for example in the presence of a cationic deposition polymer latex on the fiber material, to form a composite structure. 用这种方式,可以用本发明的特别地改性的表面构造独特的层结构。 In this manner, the surface layer structure of the unique structure of the present invention in particular is modified.

在另外的方面中,本发明还提供制品,其包括基材和沉积或布置在其上面的本文中所提供的生物活性阳离子型聚合物胶乳。 In a further aspect, the present invention also provides an article which comprises a bioactive cationic polymer latex deposited or disposed on a substrate and thereon provided herein. 对于本发明的目的,术语"基材"应该广泛地理解和解释为包括由无机材料、 有机材料、其复合材料、其混合物、或其任何类型的组合物形成的所有的那些。 For the purposes of the present invention, the term "substrate" should be broadly understood and interpreted to include all those formed from inorganic materials, organic materials, composites thereof, mixtures thereof, or any type of composition. 例如,基材可以包括但不限于纤维、填料、颜料等,以及其它有机和无机材料。 For example, the substrate may include but are not limited to, fibers, fillers, pigments and the like, as well as other organic and inorganic materials.

在本发明的一个方面中,如本文中公开的,可以使用纤维基材。 In one aspect of the present invention, as disclosed herein, can be used fibrous substrate. 术语"纤维基材"也应该广泛地解释和理解为至少包括本文中公开的所有的纤维、机织纺织品、和无纺纺织品。 The term "fibrous substrate" should be understood and interpreted broadly to include at least all of the fibers disclosed herein, woven textiles, and non-woven textiles. 因此,纤维基材可以以例如料片、纱、织物、纺织品基材等形式存在。 Thus, the fibrous substrate may be present in the form of, for example, web, yarn, fabrics, textiles and other substrates. 纤维基材的另外的实例包括但不限于天然纤维(例如棉和羊毛)到合成纤维(例如,尼龙、丙烯 Further examples of fibrous substrates include, but are not limited to, natural fibers (e.g., cotton and wool) to synthetic fibers (e.g., nylon, propylene

树脂、聚酯、氨基甲酸酯)等等。 Resins, polyesters, urethane) and the like. 可以釆用已知的施用方法来施用生物活性阳离子型聚合物胶乳,例如棒涂/刮刀涂布、浸注、背涂、印刷、作为单根纤维上的预处理、或作为成品。 Administration may preclude the use of the known methods to administer the bioactive cationic polymer latex, such as bar / knife coating, impregnation, back coating, printing, as a pretreatment on individual fibers, or as a finished product. 还如本文中使用的,术语"纺 Also as used herein, the term "spinning

织物基材"可以根据其在Krishnan等人的美国专利5, 403, "0中的应用来限定,所述专利被全文并入本文作为参考。 Fabric substrate "which may Krishnan et al., U.S. Patent No. 5, 403," 0 is defined in the application, said patent being incorporated herein by reference. 在这个方面中,例如, "纺织物基材"可以包括由本文中所述的任何纤维形成的纤维、料片、 纱、细线、条子、机织织物、针织物、无纺织物、家具装饰织物、立毛地毯、绒头地毯等,包括其任何组合。 In this aspect, for example, "textile substrate" may include fibers formed from any of the fibers described herein, the web, yarn, thread, sliver, woven fabric, knitted fabric, nonwoven fabric, upholstery fabric, piloerection carpets, carpet pile, including any combination thereof.

本发明的生物活性阳离子型胶乳组合物还可以应用于各种塑料或橡胶基材。 Bioactive cationic latex composition of the present invention may also be applied to various plastic or rubber substrate. 这种材料的实例包括但不限于日用品模压热塑性塑料例如聚烯烃;工程热塑性塑料例如聚砜、缩醛、聚碳酸酯等;热固性材料, 例如环氧树脂、氨基曱酸酯、和相关的材料;和挤出或吹塑的薄膜。 Examples of such materials include, but are not limited to, commodity molded thermoplastics such as polyolefins; engineering thermoplastics such as polysulfones, polyacetal, polycarbonate and the like; thermosets such as epoxy, amino acid esters Yue, and related materials; and film extrusion or blown. 可以将聚合物通过棒涂/刮刀涂布、喷涂、浸涂、作为挤压工艺过程中的叠层涂层、或作为在模压工艺过程中施加在模具中的涂料来施用。 The polymer can be coated by a bar / knife coating, spraying, dipping, as a laminate coating during the extrusion process, or as a coating applied in the mold during the molding process to be administered. 橡胶产品可以包括片材、挤出/模制的制品、复合材料等。 Rubber product may include sheet article extrusion / molding of composite materials. 在另一个方面中,本发明的生物活性阳离子型胶乳组合物还可以以固体形式使用。 In another aspect, the bioactive cationic latex composition of the present invention may also be used in solid form. 在这个方面中,例如,可以将本发明的胶乳凝固或喷雾干燥,以便提供固体的生物活性阳离子型胶乳,其可以以固体形式用作塑料制品中的添加剂、用于例如挤出或吹塑的工艺中、作为用于各种聚乙烯和聚丙烯等的添加剂、和用于许多其它的聚合物和塑料应用中。 In this aspect, for example, the latex of the present invention may be coagulated or spray dried to provide the bioactive cationic latex solids, which can be used as additives in plastic products in solid form, for example, extrusion or blow process, as additives for various polyethylenes and polypropylene, and for many other polymer and plastic applications.

本发明的生物活性阳离子型胶乳组合物还可以应用于各种木基材或金属基材。 Bioactive cationic latex composition of the present invention may also be applied to various metallic substrates or wood substrates. 在这个方面中,适合的基材包括各种天然的和制造的木基材。 In this aspect, suitable substrates include various natural and manufactured wood substrate. 适合的金属基材包括金属和金属合金,例如碳钢、不锈钢,并且包括实心钢条、片材、线圏、绳等等,其中通过多种工艺(例如喷涂、 浸涂、辊涂、和相关的方法)中的一种来施用组合物。 Suitable metal substrates include metals and metal alloys, such as carbon steel, stainless steel, and including solid steel bars, sheets, rings of wire, rope, etc., by a variety of processes in which (e.g. spraying, dip coating, roll coating, and related one way) in the administered composition.

在这方面,可以根据本领域技术人员已知的标准方法生产包括基材和在其上面沉积或布置有生物活性阳离子型聚合物胶乳的制品。 In this regard, according to the present art can be produced by standard methods known in the art comprising a substrate and disposed or deposited bioactive cationic polymer latex article thereon. 在另一个方面中,所述制品可以具有在其上面布置的至少一个其它聚合物层,以便形成组合结构,因此,如果期望,可以使用各种类型的多重聚合物层。 In another aspect, the article may have at least one other polymer layers disposed thereon to form a composite structure, and therefore, if desired, can use various types of multi-layer polymer. 例如,可以将各种聚合物的其它层布置在已经存在于制品中的生物活性阳离子型聚合物胶乳上,以便形成复合结构。 For example, other layers may be disposed on various polymers bioactive cationic polymer latex is already present in the article in order to form a composite structure. 在这个方面中,可以在沉积生物活性阳离子型胶乳之后沉积阴离子型胶乳或其它聚合物,以便增强制品的具体性能。 In this aspect, the anionic latex may be deposited after the deposition of a polymer or other bioactive cationic latex in order to enhance specific properties of the article. 因此,根据本发明可以生产减压特别地改性的表面的特别定制的制品。 Thus, according to the present invention can be produced specially tailored decompression particularly modified surface of the article.

在更广泛的方面中,本发明还提供覆层材料,其包括任何材料和在上面沉积或布置的生物活性阳离子型聚合物胶乳,其中可以使任选的其它材料的另外的层与本发明的生物活性阳离子型聚合物胶乳组合使用。 In its broader aspects, the present invention further provides a coating material comprising any material and a bioactive cationic polymer latex deposited thereon or arranged, which can make the additional layers of the present invention, optionally, other materials bioactive cationic polymer latex used in combination. 如本文中使用的,术语"材料"意在广泛地使用,包括但不限于任何无机材料、任何有机材料、任何其复合物、或其任何组合。 As used herein, the term "material" is intended to be widely used, including but not limited to, any inorganic material, any organic material, any composite thereof, or any combination thereof. 适合的材料的实例包括但不限于纤维、填料、粒子、颜料、其复合材料、 其组合物、其混合物等等。 Examples of suitable materials include, but are not limited to, fibers, fillers, particles, a pigment, composites thereof, combinations thereof, mixtures thereof and the like.

还可以使用多重的淀积过程来生产可在不同于纺织品和纤维材料的领域中有应用的复合薄膜。 May also be used to produce multiple deposition process can be applied in a thin film composite field is different from the textile and fiber materials. 在一个方面中,例如,本发明的生物活 In one aspect, for example, biological activity of the present invention

gloves)。 gloves). 还可以使用本文中提供的生物活性阳离子型聚合物胶乳生产纤维素结构,包括但不限于纤维素复合材料和重负荷纤维素结构。 May also be used bioactive cationic polymer latex provided herein for producing a cellulose structure, including but not limited to, cellulosic composites and heavy duty cellulosic structures. 纤维素复合材料的实例包括但不限于与过滤、鞋内底、屋面纸板、垫圏等有关的那些复合材料。 Examples of cellulosic composites include, but not limited to filtration, insole, roofing board, the pad rings of composite material like those associated. 重负荷纤维素结构包括但不限于手提袋(dunnage bags)、 工业用凸轮(industrial wipes)、和相关结构。 Heavy duty cellulosic structures include, but are not limited to the bag (dunnage bags), industrial cam (industrial wipes), and related structures. 在另外的方面中,本发明的该淀积工艺和生物活性阳离子型聚合物胶乳还可用于其它技术领域,包括但不限于絮凝剂、用于造纸的干湿两用强度添加剂、保留助剂、水泥改性、染料定色、可再分散的粉末、等等。 In a further aspect, the deposition process and bioactive cationic polymer latex of the present invention can be used in other technical fields, including, but not limited to, flocculants, wet and dry strength additives for papermaking, retention aids, cement modifiers, dye fixer, redispersible powders, and the like.

与用于制造生物活性材料的先前的方法相比较,本发明可以提供某些优点。 Compared with the prior methods for producing a biologically active material, the present invention may provide certain advantages. 在这个方面中,例如,生物活性阳离子型胶乳可以实质上沉积在基材上,使得残留的生物活性胶乳不保留在工艺流体介质中, 从环境的观点看提供了可能的优点。 In this aspect, for example, a bioactive cationic latex can be substantially deposited on a substrate, such that the biological residual active latex does not remain in the process in a fluid medium, from the viewpoint of environmental advantages may be provided. 此外,可以优选将生物活性阳离子型胶乳沉积在携带净的负电荷的任何基材上并且可以以均匀的方式进行沉积,从而使用较少的胶乳聚合物。 Further, preferably the bioactive cationic latex deposited on any substrate carry a net negative charge and can be deposited in a uniform manner, thereby using less latex polymer. 仍在这个方面中,并且不打算束縛于理论,认为生物活性阳离子型胶乳能够在带负电的基材上形成实质上均匀的聚合物材料单层,从而允许使用较少的胶乳提供期望的覆盖。 Still in this aspect, and it is not intended to be bound by theory, that the bioactive cationic latex capable of forming substantially uniform monolayers of polymer material on a negatively charged substrate, thereby allowing the use of less latex to provide the desired coverage. 因为生物活性阳离子型胶乳可以由现有的乳液聚合工艺形成, 该制造方法有利地允许制备高分子聚合物。 Since bioactive cationic latex can be formed by a conventional emulsion polymerization process, the manufacturing method advantageously allows the preparation of polymers.

本文中公开的生物活性阳离子型聚合物胶乳还可以排除对阳离子保留助剂和阳离子型表面活性剂的需要。 Bioactive cationic polymer latex disclosed herein may also preclude the need for cationic retention aids and cationic surfactants. 在一个方面中,例如,生物活性阳离子型聚合物胶乳可以实质上不含阳离子型表面活性剂。 In one aspect, for example, a bioactive cationic polymer latex may be substantially free of cationic surfactant. 这种特征可能是特别合乎需要的,因为阳离子型表面活性剂通常不能很好地保留并且可能在含水环境中引起泡沫和其它不利影响。 This feature may be particularly desirable because cationic surfactants generally not well retained and can cause foaming and other adverse effects in an aqueous environment. 然而,在另一个方面中,本发明还提供了使用可以表现出阳离子型表面活性剂性能的生物活性剂和/或使用保留助剂。 However, in another aspect, the present invention also provides the use of an agent can exhibit cationic surfactant properties bioactive agent and / or retention aid. 此外,如果期望,聚合物胶乳可以不含常规的表面活性剂,包括例如非离子型表面活性剂。 Further, if desired, the polymer latex can be free of conventional surfactants including, for example non-ionic surfactants.

如本文中提供的,可以使用本领域技术人员公知的各种技术将本发明的胶乳组合物应用于各种基材。 As provided herein, various techniques well known to those skilled in the latex composition of the present invention is applied to various substrates. 结果是,本发明有许多应用,其中有许多提供在以下的列表中。 As a result, the present invention has many applications, many of which are provided in the following list. 在这个方面中,尽管这个列表不是详 In this aspect, even though this list is not detailed

尽的,具体的应用包括但不限于:纺织品,例如民用和商用的地毯或瓷砖;用于HVAC或真空吸尘器、或汽车应用的液体和空气过滤器;医用手术袍、布帘、敷料、覆盖物等等;用于服装、装璜、床单、毛巾等的纤维、印刷或染色的织物的预处理;尿布和失禁制品;汽车内部应用,例如装饰、内部装饰、地席、过滤器、等等;室内装潢涂层; 层压和结合粘合剂;用于吸收声音的泡沫;泡沫制品,例如枕头和床垫;用于食品加工等的带或其它机械部件;胶带,例如蒙面胶带、手术胶带、工业胶带、等等;电气、工业和家庭用清理擦、布、和海绵; 鞋产品,例如鞋内底、皮鞋包头、等等;塑料和/或橡胶制品,例如工具把手、工具手柄、玩具、橡皮手套、片材、或其它制品;机器外壳, 例如用于电脑、显示器和诊断设备或仪器的机器外壳;医疗器材,例 Do, specific applications include, but are not limited to: textiles such as residential and commercial carpets or tiles; a HVAC or vacuum cleaners, or the liquid and air filters for automotive applications; medical surgical gowns, drapes, dressings, covers and the like; fibers used in clothing, decoration, sheets, towels and the like, pre-printed or dyed fabric; diapers and incontinence products; automotive interior applications, e.g. decoration, interior decoration, mats, filters, and the like; upholstery coatings; laminating and bonding adhesives; foam for sound absorption; foam article, such as pillows and mattresses; like belt used in food processing or other mechanical components; tape, tape masked e.g., surgical tape , industrial tape, and the like; electrical, industrial, and household cleaning wipe, cloth, sponge; footwear, the insole e.g., header shoes, and the like; plastic and / or rubber articles, such as tool handles, tool handles, toys , rubber gloves, sheets, or other articles; machine housing, for example, a housing for the machine computer, display and diagnostic devices or instrumentation; medical equipment, cases 导管、气球、管子、注射器、诊断组件、等等;包装或产品保护, 如应用于易腐物质、计算机外围设备、半导体、存储芯片、CD、 DVD、 等等;用于丙烯树脂、聚碳酸酯等等的沖击改性剂;用于手套的overdips或underdips,例如用于清洁房间的手套;透气薄膜;用于防渗剂(antipenetrant);砧板;用于包装的挤出和吹塑的薄膜;纸制品,例如真空袋、书皮、空气过滤器、液体过滤器、 墙面涂料、干湿两用擦、纸巾(tissues)、等等;用于乙烯基地毯的毡; Catheters, balloons, tubing, syringes, diagnostic component, and the like; packaging or product protection, as applied to perishables, computer peripherals, semiconductors, memory chips, CD, DVD, and the like; propylene resins, polycarbonate impact modifiers and the like; overdips underdips or for gloves, for example, a glove of clean room; breathable film; impermeable to agent (antipenetrant); anvil; for packaging and blown film extrusion ; paper products such as vacuum bags, book covers, air filters, liquid filters, wallcoverings, wet and dry rubbing, tissue (Tissues), and the like; vinyl carpet for carpet;

模制用浆应用;包装例如箱子、纸板箱、模制品、和相关物品;用于礼品包装的施胶压榨涂层(size press coatings)、喷墨介质、可呼吸 Molding the paste application; e.g. packaging boxes, cartons, molded articles, and related items; gift wrap for size press coating (size press coatings), ink jet media, breathable

涂层、等等;纸中的湿部添加剂、胶带、用于掩模的标记、手术应用、 通用应用、等等;在纸中使用的粘合剂;在墙板例如石膏墙板中使用的粘合剂等等;在胶带中使用的粘合剂、标记、贴花印刷、薄膜、装订、压敏应用、软包装和复合粘合剂(FPLA)、等等;无机和/或有机的材料,例如填料或颜料的涂层或包封、建筑密封材料和灰浆、石膏墙板涂层或粘合剂、外部或内部涂层、等等;瓷砖粘合剂;在医院、清洁室、诊所、学校、和相关环境中使用的地面涂料;用于医院和医疗环境的涂料;吊顶板材;玻璃纤维涂料,例如玻璃垫、绝缘材料、过滤材料、增强的复合材料、等等;用于空调或制冷盘管的涂层;用于空调系统、换热器、离子交换器、包括冷却水处理在内的水处理系统、 太阳能单元、涂层管、等等的其它部件;厨房物品;卫生设备的组件 Coating, and the like; wet end additives in paper, tapes, marked for the mask, surgical applications, general purpose applications, and the like; binders used in the paper; gypsum wallboard, for example, used in the wallboard adhesive or the like; adhesive tapes for use in the marker, decals, films, stapling, pressure sensitive applications, flexible packaging and adhesive composite (the FPLA), and the like; inorganic and / or organic material, e.g. fillers or pigments coating or encapsulation, building sealants and mortar, gypsum wallboard coatings or binders, exterior or interior coatings, and the like; tile adhesive; in hospitals, clean rooms, clinics, schools, and floor coating used in relation to the environment; paints for hospitals and medical environments; ceiling tile; glass fiber coatings such as glass mats, insulation, filter materials, reinforced composites, and the like; for air conditioning or refrigeration coils coatings; other components for air conditioning systems, heat exchangers, ion exchangers, including cooling water systems, including water treatment, solar units, coated pipes, and the like; kitchen articles; sanitary equipment components 水系统的部件;装置的操作者单元例如触板;用于浴室的材料例如淋浴挂帘、固定物、卫生间物品、甚至是接合或密封复合物;卫生器材, 例如用在用于支架、植入物、假体、导管、管子、隐形眼镜、隐形眼镜清洁剂或存储溶液、保护性薄膜或背膜、医疗器械、和其它卫生器材的涂层中用于提供生物活性剂的持续作用;由大量的人接触的制品, 例如电话送受话器、扶梯扶手、门把手、窗钩、用于公共交通工具的抓握带和握柄、等等;伤口或手术处理;伤口或外科绷带,包括伤口或外科绷带的任何层例如吸收剂层;医疗或运动的胶带;手术床单; 用于粘着卫生器材的胶带或标签,例如传感器、电极、造口术器械、 等等;液体消毒剂和清洁剂;个人护理或卫生产品,例如洗发剂、洗液、霜剂、头发和皮肤护理产品、沐浴液(body wash)、化妆品、卫生 Water system components; operator of the apparatus, for example, a touch panel unit; for example bathroom shower curtain material, fixtures, toilet items, and even joining or sealing compounds; medical devices, for example in stent implantation was prostheses, catheters, tubing, contact lenses, contact lens cleaners or storage solutions, protective film or the backing film, medical equipment, medical devices and other coatings for providing a sustained action of bioactive agents; by a large human contact with the product, such as a telephone handset, escalator handrails, door handles, window hook, and a grip for gripping with public transport, and the like; treatment or surgical wounds; surgical wounds or bandages comprising a surgical wound or any layer, such as an absorbent layer of the bandage; or medical tape movement; surgical sheets; medical devices for the adhesive tape or label, such as sensors, electrodes, ostomy equipment, and the like; liquid disinfectants and cleaners; personal care or hygiene products, such as shampoos, lotions, creams, hair and skin care products, bath gel (body wash), cosmetics, health 间物品、等等;除地板以外的表面的卫生涂层,例如在医院、诊所、 学校、居家、办公室等;施用于墙壁、天花板、地板、拒台、等等的硬的和多孔性表面涂层;装饰用混凝土;木材例如定向结构板(oriented strand board, 0SB)涂层;曱板和用于涂层或浸注的建筑材料;复合结构材料;家具涂层;卫生涂层,例如用于桌面、柜台、 门把手、门拉手、固定物、等等;地板应用,例如用于层压板、硬木地板、和其它复合地板材料;装饰性层压板,例如桌面、柜台、家具、 等等;其它建筑材料,例如屋面材料、墙壁材料、立面、围墙、或用于木材保护应用;海运应用,例如用于艇身、码头、救生圏、钻井平台、或压载水槽;金属,例如橱拒、门把手、手柄、固定物、等等; 和家具、用作器具的涂层、初始设备制造(OEM)、等等。 Between items, and so on; health coating surface other than the floor, for example in hospitals, clinics, schools, home, office and so on; and hard-coated porous surface applied to walls, ceilings, floors, reject station, etc. layer; decorative concrete; Yue building materials for the coating or plate, and the impregnation;; e.g. wood OSB (oriented strand board, 0SB) coated composite structural material; furniture coating; health coating, for example, table, counter, door handles, door handles, fixtures, and the like; flooring applications, for example, laminates, hardwood flooring, and other composite flooring materials; decorative laminates, such as a table, counter, furniture, and the like; other construction materials such as roofing material, wall material, facades, fencing, or for wood protection applications; marine applications, for example for hull, pier, rings of rescue, drilling platforms, or ballast water tank; metals, e.g. cabinet refused, door handles, handles, fixtures, and the like; and furniture, coatings as appliances, original equipment manufacturer (OEM), and the like.

在这个方面中,本发明的抗微生物制剂可以用作生物污垢抑制剂, 特别是用于冷却回路中。 In this aspect, the antimicrobial formulations of the invention may be used as a biofouling inhibitor, in particular for the cooling circuit. 为了阻止藻类或细菌蔓延引起的对冷却回路的损害,所述回路典型地必需经常清理或者是适当地大于正常尺寸的。 In order to prevent the spread of bacteria algae or damage caused by the cooling circuit, the circuit is typically necessary to regularly clean or suitably larger than the normal size. 在发电厂和化学工厂中通常发现的开放式冷却系统中,添加抗微生物物质例如福尔马林通常是不可能的。 Open cooling system in power plants and chemical plants typically found in the addition of antimicrobial substances such as formalin is usually impossible. 其它抗微生物物质经常是腐蚀性很强或形成泡沫,阻止了其在这类系统中的应用。 Other antimicrobial substances are often highly corrosive or form foams, preventing their use in such systems. 因此实际上抑制了细菌或藻类在所述系统的部件上的沉积。 So actually inhibit bacteria or algae on components of the deposition system. 因此,本发明的制剂和材料在这种应用中很有用。 Thus, the formulations and materials of the present invention are useful in such applications.

在另一个方面中,本发明还可以提供通过向冷却水中添加分散形式的抗微生物制剂将冷却水流或水处理系统灭菌的方法。 In another aspect, the present invention can also provide a method by adding antimicrobial formulation in dispersed form to the cooling water system is cooling water or sterilized water. 所述分散形式可以直接在制备过程中得到,例如通过本文中详述的乳液聚合,也可以通过沉淀聚合、或悬浮聚合,或随后将通过任何这些方法中得到的抗微生物聚合物在例如喷射磨中碾磨。 The dispersed form can be obtained directly during the manufacturing process, for example by emulsion polymerization as detailed herein, also by precipitation polymerization, or suspension polymerization, or subsequently by a jet mill, for example, antimicrobial polymer obtained in any of these methods milled.

本发明的抗微生物胶乳聚合物可以作为涂料组合物施用或应用, 其可以用于与要求抗微生物作用有关的各种目的。 The antimicrobial latex polymer of the present invention may be administered as a coating composition or application, which can be used with antimicrobial effect required for various purposes related. 例如,在一个方面中,本文中公开的抗微生物胶乳聚合物可以用于各种隔离材料,例如用于管道的包裹材料,所述管道特别是具有细菌腐蚀危险的。 For example, in one aspect, disclosed herein, the antimicrobial latex polymers may be used in a variety of insulating material, for example for pipe wrapping material, in particular with the conduit the risk of corrosion of the bacterium. 因此, 本发明的材料在与弹性体隔离材料结合时是有用的。 Accordingly, the material of the present invention, when combined with an elastomeric insulation material is useful. 这种涂料组合物还可以用于工业绝缘材料,例如用于隔离管道(其实例是加热管),和用于隔离阀门和导管。 The coating compositions may also be used for industrial insulating materials, for example for insulating duct (examples of which are heating pipes), and the isolation valve for the conduit. 此外,本文中公开的抗微生物胶乳可与用于许的隔离材料结合。 Further, it disclosed herein may be combined with the antimicrobial latex material for the isolation of many. 本文中提 Mention this article

料结合。 Material combination. 包括本发明的抗微生物胶乳的这种涂层还可以用作用于空调装置、冷凝器、冷藏库、和其它冷藏单元、以及其零件的涂层,以及用作海运船舶和用于木材防腐的油漆的涂料组分。 Include antimicrobial latex of the present invention may also be used for this coating the coating air conditioner, a condenser, a refrigerator and other refrigeration units, and parts thereof, as well as for ships and ocean wood preservative paint the coating composition. 包括本发明的抗微生物胶乳的涂层还可以用作例如金属、塑料、或陶器的基材的涂层, 用于卫生设备、医院,或用于食品工业,或可能容易地传播感染性病原体的任何类型的涉及频繁接触的任何制品,例如门拉手、卫生设备、 开关和手柄。 Include antimicrobial latex coating of the present invention may also be used as a coating for example metal substrates, plastics, ceramics, or for sanitary, hospital, or for the food industry, or may be easily spread of infectious pathogens It relates to any type of frequent contact with any articles, such as door handles, sanitary fittings, switches, and the handle. 在这种涂层的情况中,使用粉末涂料形式的涂料组合物可能是有利的。 In the case of such a coating, a powder coating composition in the form of coatings may be advantageous.

抗微生物胶乳对卫生器材的施用 Antimicrobial latex administration of health equipment

本文中使用的属于"卫生器材"是指被插入到哺乳动物体内的、 Belonging used herein, "medical devices" refers inserted into a mammal,

何材料。 Any material. 适合于本发明的抗微生物胶乳和组合物的应用的特定卫生器材包括但不限于可从外周插入的中央静脉导管、透渗析导管、长期的有通道的中央静脉导管、长期的无通道的中央静脉导管、外周的静脉 Suitable for the present invention is antimicrobial latex and compositions application specific medical devices include, but are not limited to be inserted from the outer periphery of central venous catheters, dialysis catheters, long term with a channel of a central venous catheter, long term NON central venous catheters, peripheral venous

导管、短期的中央静脉导管、动脉插管、肺动脉Swan-Ganz导管、导尿管、人造的尿括约肌、长期尿道装置、尿道扩张器、尿道支架、其它尿道装置、与组织结合的尿道装置、阴茎假体、血管移植物、血管导管端口、血管扩张器、血管外扩张器、血管支架、血管外支架、伤 It means urinary catheters, short-term central venous catheters, arterial, pulmonary artery Swan-Ganz catheters, urinary catheters, artificial urinary sphincters, long term urinary devices, urinary dilators, urinary stents, other urinary devices, tissue-bound, penis prostheses, vascular grafts, vascular catheter ports, vascular dilators, extravascular dilators, vascular stents, extravascular stents, wound

口引流管、脑积水旁路、心室导管、腹膜导管、起搏器系统、小的或临时的关节置换、心脏瓣膜、心脏辅助医疗装置等等、骨假体、人工关节、假牙、等等。 Port drainage tube, hydrocephalus shunt, ventricular catheters, peritoneal catheters, pacemaker systems, small or temporary joint replacements, heart valves, cardiac assist devices and the like, bone prostheses, artificial joints, false teeth, etc. .

在一个方面中,可以与本发明的生物活性阳离子型胶乳结合使用的卫生器材包括但不限于非金属材料,例如热塑塑料或聚合物材料。 In one aspect, the medical devices may be used in combination with the bioactive cationic latex of the present invention include, but are not limited to non-metallic materials, such as thermoplastic or polymeric materials. 这种材料的实例包括橡胶、塑料、聚乙烯、聚氨酯、硅氧烷、Gortex™ (聚四氟乙烯)、Dacron™ (聚对苯二曱酸乙二醇酯)、聚氯乙烯、Teflon™ (聚四氟乙烯)、弹性体、尼龙和用明胶、胶原或白蛋白密封的Dacron1 Examples of such materials include rubber, plastic, polyethylene, polyurethane, silicone, Gortex ™ (polytetrafluoroethylene), Dacron ™ (polyethylene terephthalate Yue glycol acrylate), polyvinyl chloride, Teflon ™ ( polytetrafluoroethylene), elastomers, nylon and gelatin, collagen or albumin sealed Dacron1

TM用于涂覆卫生器材的每种生物活性阳离子型胶乳的量可以在一定程度上改变,但是至少是足以形成有效浓度以抑制细菌和真菌生物生长的量。 The amount of each bioactive cationic latex used to coat medical devices TM may vary to some extent, but is at least sufficient to form an amount effective concentration to inhibit the growth of bacterial and fungal organisms.

抗微生物胶乳可以单独使用或者以其两种或更多种组合使用。 The antimicrobial latex may be used alone or in combination of two or more thereof. 每种抗微生物胶乳可以包括本文中提供的一种或多种抗微生物组分。 The antimicrobial latex may each include one or more antimicrobial components provided herein. 本文中公开的任何应用或用途可以另外包括将至少一种生物活性胶乳连同至少一种可以在卫生器材的整个表面分散的其它抗微生物剂。 Any application or use disclosed herein can further comprise at least one biologically active latex in conjunction with at least one other antimicrobial agents may be the entire surface of medical devices dispersed. 用于浸渍卫生器材的每种生物活性胶乳和每种抗微生物剂的量可以在一定程度上改变,但是至少是足以形成有效浓度以抑制细菌和真菌生物生长的量。 And the amount of each used to impregnate the medical devices of each latex bioactive antimicrobial agent may vary to some extent, but is at least sufficient to form an amount effective concentration to inhibit the growth of bacterial and fungal organisms.

在一个方面中,抗微生物剂可以选自抗生素、防腐剂、杀菌剂、 或其任何组合。 In one aspect, the antimicrobial agent may be selected from antibiotics, antiseptics, bactericides, or any combination thereof. 在另一个方面中,抗微生物剂可以是抗生素,包括但 In another aspect, the antimicrobial agent may be an antibiotic, including, but

不限于青霉素、头孢菌素、碳青霉烯类、其它(3-内酰胺抗生素、氨基糖甙类、大环内酯、林可酰胺类、糖肽、四环素、氯霉素、2-羟基喹啉、梭链孢素、磺酰胺、甲氧节啶、利福霉素、喁唑烷类(oxalines)、 链阳性菌素、脂肽、酮内酯类、多烯、吡咯、棘球白素、或其任何组合。 Are not limited to penicillin, cephalosporins, carbapenems, other (3-endo-lactam antibiotics, aminoglycosides, macrolides, lincosamides, glycopeptides, tetracyclines, chloramphenicol, 2-hydroxy-quinoline morpholine, fusidic element, sulfonamide, methoxy section piperidine, rifamycin, oxazolidine-based breathing of fish (oxalines), streptogramins, lipopeptides, ketolides, polyenes, azoles, echinocandins , or any combination thereof.

在一个方面中,可以使用本文中提供的生物活性胶乳将至少一种药物施加到卫生器材中,并且与可以粘着于生物活性胶乳而不是被生物活性胶乳包封的药物组合使用。 In one aspect, a biologically active latex can be used herein, provided at least one drug is applied to the medical devices, and the adhesive may be used instead of bioactive latex encapsulated biologically active latex pharmaceutical compositions. 例如,阳离子型抗微生物胶乳涂层可以作为涂层对可能具有离子电荷的卫生器材施用。 For example, the cationic antimicrobial latex coating can be applied as a coating on medical devices may have an ionic charge of administration. 随后,可以将具有互补电荷的药物施用于对器材的表面施加的带电涂层,并且可以在带电涂层与药物彼此接触时结合于所述表面。 Subsequently, the drug may be administered to have a complementary charge on the charged surface of the coating material applied to, and can bind to the surface of the charged coating and the drug in contact with each other. 药物和涂层之间的结合强度可用于影响从器材表面释放药物的容易程度。 Bonding strength between the drug and the coating can be used to affect the ease of release of the drug from the device surface. 在一个方面中,本发明提供为选择的解剖学位置递送具有这种药物递送特征的植入物或卫生器材。 In one aspect, the present invention provides for the delivery of the selected anatomical location having this drug delivery feature implant or medical devices. 在这个方面中,典型地,使用的药物包括但不限于抗微生物和抗生素,例如新霉素和磺胺类药物、抗炎药例如栽体抗炎药或非甾体抗炎药、或其组合。 In this aspect, typically drugs used include, but are not limited to, antimicrobials and antibiotics such as neomycin and sulfa drugs, anti-inflammatory agents such as antiinflammatory drugs or plant steroidal antiinflammatory drugs, or combinations thereof.

尽管可以将与本文中所述那些相似或等价的任何方法、装置、和材料用于本发明的实践或试验,但是在本文中描述了典型的方法、装置和材料。 Although described herein may be any methods similar or equivalent to, devices, and materials used in the practice or testing of the present invention, but describes the typical methods, devices and materials are herein. 在本文中提及的所有的出版物和专利都被用于描述和公开的目的并入本文,例如在出版物中描述的可以用于与本发明结合的构造和方法。 All publications and patents mentioned herein are for purposes of description and are incorporated herein disclosed, for example, described in the publication may be used in conjunction with the construction and method of the present invention. 提供本文中讨论的出版物只是表示其公开在本申请的提交日之前。 The publications discussed herein are provided only that its disclosure prior to the date of filing this application. 不应理解为发明人承认这种公开为本发明的现有技术。 This should not be construed as admissions of prior art disclosed in the present invention, as inventors.

在申请人公开或要求保护任何类型范围时,例如温度的范围、浓度的范围、原子数的范围、重量百分比等,申请人的目的是公开或要求保护这种范围可以合理地包括的每个可能的数字,以及其中包括的任何子区间和子区间的组合。 When Applicants disclose or claim a range of any type, for example, a temperature range, the range of concentrations, a range of atomic number, weight percentages, etc., Applicant's intent is to disclose or claim such a range could reasonably included each possible figures, and combinations of any sub-range and subranges encompassed therein. 因此,在申请人公开或要求保护具有若干碳原子的化学基团时,申请人的目的是,按照本文中的公开,公开或要求保护这种数值范闺可以包括的每个可能的数字、子区间、和子 Thus, when the Applicants disclose or claim a chemical group having a number of carbon atoms, Applicants intend to, in accordance with the disclosure herein disclosed or claimed for each possible number that such numerical range may be included Gui, sub range, and child

区间的组合。 Combination interval. 例如,R选自具有最多12个碳原子的烷基基团的公开, 或者如本文中使用的d-d2烷基基团的替换表达方式,是指可以选自具有l、 2、 3、 4、 5、 6、 7、 8、 9、 10、 11、或12个碳原子的烷基基 For example, R is selected from alkyl groups having disclosed up to 12 carbon atoms, or alternatively as the expression d-d2 alkyl group as used herein, refers to a selected may have l, 2, 3, 4 , 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms, alkyl of

团,以及这两个数字之间的任何范围,例如C3-Cs烷基基团,并且还包 Group, and any range between these two numbers, for example C3-Cs alkyl group, and further

括这两个数字之间的范围的任何组合,例如CfCs和C7-d。 Including any combination of the range between these two numbers, e.g. CfCs and C7-d. 烷基基团。 Alkyl group. 因此,申请人保留如下的权利,即,术语例如"具有最多12个碳原子的基团"用这种范围可以合理地包括的任何单个数字、以及其中包括的任何子区间和子区间的组合来替换。 Accordingly, the applicant reserves the rights below, i.e., terms such as "group having up to 12 carbon atoms" with any single number that such a range could reasonably encompass, as well as any sub-range, and combination of subranges encompassed therein replaced . 在另一个实例中,公开摩尔比率典型地为约0. 1-约1. 0,申请人的目的是表示该摩尔比率可以选自约0.1:1、约0.2:1、约0.3:1、约0.4:1、约0.5:1、约0.6:1、 约0.7:1、约0.8:1、约0.9:1、或约1.0:1,以及其中包括的任何子区间和子区间的组合。 In another example, the disclosed molar ratio is typically from about 0. 1 to about 1.0, Applicants intend to indicate that the selected molar ratio can be from about 0.1: 1, about 0.2: 1, about 0.3: 1, about 0.4: 1, about 0.5: 1, about 0.6: 1 composition, and any sub-range comprised therein and subranges: 1, about 0.7: 1, about 0.8: 1, about 0.9: 1, or about 1.0. 类似地,公开特定的重量%可以为约80重量%-约90重量%,申请人的目的是表示该重量百分比可以是约80重量%、 约81重量%、约82重量%、约83重量%、约84重量%、约85重量%、约86重量%、约87重量%、约88重量%、约89重量%、或约90重量%。 Similarly, the particular disclosed wt% may be from about 80 wt% - about 90 wt%, Applicant's intent is that the weight percent can be from about 80 wt%, from about 81 wt%, from about 82 wt%, from about 83 wt% , from about 84 wt%, from about 85 wt%, from about 86 wt% to about 87% by weight, from about 88 wt%, from about 89 wt%, or from about 90 wt%.

申请人保留带条件排除或排除任何这种组的任何单个成员的权利,包括该组内的^f壬何子区间或子区间的组合,其可以是以范围或以页任何类似的方式要求保护的,如果由于任何原因出现这种情况,申请人选择要求保护小于该公开的完整范围,例如由于在提交本申请时申请人没注意到的参考文献。 Applicants claim the conditional exclusion or exclude any individual members of any such group is retained, including any combination of non ^ f subinterval or subintervals within the group, which may be a range or in any similar manner page claimed if this is the case for any reason applicants choose to claim less than the full scope of the disclosure, for example, since the time of filing the present applicant not noticed by reference. 另外,申请人保留带条件排除或排除要求保护的组的任何单个的取代基、添加剂、化合物、单体、表面活性剂、 结构等、或其任何组合、或任何单个成员的权利,如果由于任何原因出现这种情况,申请人选择要求保护小于该公开的完整范围,例如由于在提交本申请时申请人没注意到的参考文献。 Further, Applicants reserve any individual with exclusion of groups or exclude claimed substituents, additives, compounds, monomers, surfactants, structures, etc., or any combination thereof, as claimed in any individual member or, if for any the reason for this, applicants choose to claim less than the full scope of the disclosure, for example, since the time of filing the present applicant not noticed by reference. 对于本文中公开的任何特定的化合物,提供的任何一般公开或结构还包括所有的异构体,例如构象异构体、区域异构体、立体异构体等,其可以产生自特定的取代基组。 For any particular compound disclosed herein, any general disclosure or structure provided includes all isomers, such as conformational isomers, regioisomers, stereoisomers and the like, which may be produced from a particular substituent group. 一般结构还包括所有的对映异构体、非对映体、和对映体形式或是消旋体形式的其它光学异构体、以及立体异构体的混合物,如上下文需要的。 The general structure also encompasses all enantiomers, mixture of diastereomers thereof, optical isomers, and the other enantiomeric form or racemic form, and stereoisomers, as the context requires. 通过以下实施例进一步说明本发明,不应将其看作是以任何方式对本发明的范围产生限制。 By the following examples further illustrate the present invention and should not be considered in any way a limitation on the scope of the present invention. 相反地,应该清楚地理解,在阅读本文中的说明之后,本领域技术人员可以想到本发明的各种其它方面、实施方案、改进和等价物,其并不脱离本发明的精神实质或随后要求保护的范围。 On the contrary, it should be clearly understood that, after reading the description herein, those skilled in the art may devise various other aspects, embodiments of the present invention, modifications and equivalents thereof, without departing from the spirit of the invention or subsequently claimed range. 在以下实施例中,除非另作说明,试剂得自商业来源。 In the following examples, unless otherwise specified, reagents were obtained from commercial sources. 包括阳离子型聚合物胶乳的一般合成试验方法的一般程序提供在Krishnan的美国专利申请公布2005/0065284和2005/0003163中,其各自被全文并入本文作为参考。 General procedure for the synthesis test method generally comprises a cationic polymer latex provided Krishnan U.S. Patent Application Publication 2005/0065284 and 2005/0003163, each of which is incorporated herein by reference. 实施例1遞i2Sf欢//入^#活^^辨务#^參活#/^溥子费應#乙向1加仑的反应器加入以下成分:约1142 g水;约5.95 g非离子型表面活性剂Abex™25" (Rhodia);约11.90 g甲氧基聚乙二醇曱基丙烯酸酯(MPEG 550,得自Cognis);和约31.7 g曱基氯季铵化的甲基丙烯酸二甲基氨基乙基酯(AgeflexTMFM1Q75MC,得自Ciba Specialty Chemicals)。然后通过使反应器内容物经过几个真空/K反应器加入约59.5 g丙烯酸丁基酯和约119g苯乙烯。使反应器再次经过几个真空/N2填充循环,之后将反应器内容物的温度提高到约165° F,这时将约23.80 g水和约2.38 g W0K0 V-50 (WOKO Chemicals)的引发剂溶液注入到反应混合物中。将反应混合物在约165° F保持大约30分钟,然后开始将以下原料进料到反应器中。在30分钟的"保持期"之后,可以将以下组分进料到反应器中:1) 由约238 g 丁二烯组成的丁二烯原料,在约5小时内进料;2) 约102 g丙烯酸 Example 1 into a delivery i2Sf Huan @ ^ # ^ # live traffic parameters identified ^^ live # / Pu ^ # B sub fee shall be the following ingredients were added to 1 gallon reactor: about 1142 g of water; about 5.95 g non-ionic surfactant Abex ™ 25 "(Rhodia); from about 11.90 g of methoxy polyethylene glycol Yue acrylate (MPEG 550, available from Cognis); and about 31.7 g Yue chloride quaternized dimethylaminoethyl methacrylate aminoethyl (AgeflexTMFM1Q75MC, available from Ciba Specialty Chemicals). then the reactor contents was subjected to several vacuum / K reactor was added about 59.5 g of butyl acrylate and about 119g of styrene. The reactor again after a few vacuo / N2 fill cycles, after which the temperature of the reactor contents was raised to about 165 ° F, a time of about 23.80 g of water and about 2.38 g W0K0 V-50 (WOKO Chemicals) initiator solution is injected into the reaction mixture. the reaction the mixture was kept for about 30 minutes at about 165 ° F, and then start the following raw materials fed into the reactor after 30 minutes of "holding period", the following components may be fed into the reactor: 1) of about 238 g butadiene butadiene feed, feed about 5 hours; 2) from about 102 g acrylic acid 基酯、约517 g苯乙烯、和约119 g任何适合的生物活性剂(例如本文中公开的那些)的混合单体原料。整个混合物的总的进料时间可以是约5小时。可以在混合单体原料进料约1 小时之后将生物活性成分引入到混合单体原料中,其涉及将约119 g 的生物活性剂溶解于在混合单体原料的后4个小时进料时间内引入到反应器中的约495 g的苯乙烯/丙烯酸丁基酯单体混合物中;3) 由约152 g水、约47. 60 g MPEG 550 (Cognis)、约47. 60 g 甲基氯季铵化的甲基丙烯酸二曱基氨基乙基酯(AGEFLEX™ FM1Q75MC, 得自Ciba Specialty Chemicals)、和约74.5 g的7V"羟曱基丙蜂酰胺组成的含水单体原料。 Ester, from about 517 g styrene, about 119 g of any suitable bioactive agent (such as those disclosed herein) mixed monomer feed. The total feed time of the entire mixture may be about 5 hours can be mixed single after the raw material feed for about one hour into the biologically active ingredient into the mixed monomer feed, which involves approximately 119 g of the bioactive agent introduced into the reactor dissolved in a mixed monomer feed within the feed time of 4 hours about 495 g of a styrene / butyl acrylate monomer mixture; and 3) consisting of about 152 g of water, about 47. 60 g MPEG 550 (Cognis), about 47. 60 g of methyl chloride quaternary ammonium methyl Yue-yl group acrylic acid aminoethyl ester (AGEFLEX ™ FM1Q75MC, available from Ciba Specialty Chemicals), and about 74.5 g of 7V "hydroxyalkyl Yue propionic amides bee aqueous monomer feed. 可以在大约3小时的时间内将这个含水单体原料进料到反应器中;和4) 由约202 g水和约4. 8 g的WOKOTM V-50组成的含水引发剂原料,可以在约5.5小时内将其进料到反应器中;在完成原料的加入时,继续反应,直到大部分(大于约98%)的单体已经反应。 It may be within about 3 hours the aqueous monomer feed fed to the reactor; 4 and about 202 g of aqueous water and about 4. 8 g of WOKOTM V-50 composition) initiator feed, may be from about 5.5 hours it is fed to the reactor; upon completion of addition of the raw materials, the reaction was continued until most (greater than about 98%) of the monomers have reacted. 然后使反应器内容物冷却下来并且真空汽提,以除去未反应的单体和增加固体含量到约40重量%。 Then the reactor contents were cooled down and the vacuum stripped to remove unreacted monomers and increase the solids content to about 40 wt%. 如有必要或期望,可以在汽提反应挥发物之前根据需要调节胶乳的pH。 If necessary or desired, the latex may be mentioned pH adjustment prior to the reaction of volatiles in the vapor as necessary. 实施例2遞i^e^〃入^參活^浙新备^^樹活^/^庠子曹應^可以根据实施例2中提供的细节进行乳液聚合反应,不同之处在于在5小时的苯乙烯/丙烯酸丁基酯进料的约4小时之后将大约49 g 生物活性组分样品引入到混合单体物流中。 Example 2 delivery into 〃 i ^ e ^ ^ ^ Zhejiang new parameters live live tree Preparation ^^ ^ / ^ ^ Cao Xiang sub emulsion polymerization reaction can be carried out according to the details provided in Example 2, except that 5 hours styrene / butyl acrylate feed after about 4 hours about 49 g of active ingredient biological sample into the mixed monomer stream. 这个工艺包括将生物活性剂溶解于在混合单体原料的最后1小时进料时间内被引入到反应器中的约124 g苯乙烯/丙烯酸丁基酯单体混合物中。 This process comprises dissolving the biologically active agent is introduced into about 124 g of styrene in the reactor / butyl acrylate monomer mixture in the last hour of the mixed monomer feed the feed time. 实施例3潜合才戎^ ^浙# /斤庠f的#斧确定抗真菌墙板作为评价结合有抗真菌剂的阳离子型胶乳的对象。 ^ # ^ Zhejiang only Rong / kg the Xiang f 3 Example # ax engagement latent embodiment determines the object as the evaluation panels antifungal cationic latex incorporating an antifungal agent. 这个实施例的目的是通过在用于生产纸的常规湿部工艺中将阳离子型聚合物并入到石膏墙板的纸面层(paper facing)中来递送抗真菌剂。 This object is achieved by an embodiment the cationic polymer portion in the conventional wet process for producing a gypsum wallboard paper is incorporated into the paper layer (paper facing) to deliver the antifungal agent. 通过在聚合工艺过程中将不同的抗真菌添加剂以不同的水平并入到聚合物中生产了几种阳离子型聚合物。 Different levels of additives incorporated in a polymerization process by different antifungal produced several polymer to cationic polymer. 将聚合物作为纸上的涂层以及通过在湿部工艺中加入来进行试验。 The polymer coatings on paper as well as tests carried out by the addition of the wet end process. 主要的抗真菌评价是基于ASTM G-21和ASTM D-3273进行的,表明使用两种抗真菌添加剂(丙环唑("PZ")和戊唑醇("TZ"))的组合得到最好的抗真菌结果。 The main antifungal evaluations based on ASTM G-21 and ASTM D-3273 for, indicating the use of two antifungal additives (propiconazole ( "PZ") and tebuconazole ( "TZ")) to give the best combination of antifungal results. 涂层研究显示,基于湿重的0. 4%的PZ/TZ水平具有显著的抑制效果,而且PZ/TZ可以通过湿部和干净地沉积在纸上来输送。 Coatings showed a significant inhibitory effect on a wet weight of 0.4% of the PZ / TZ level, and PZ / TZ could be transported through the wet end and paper cleanly deposited. 使用AATCC-100方法对一系列阳离子型聚合物(没有任何添加剂并入到聚合物中)评价抗细菌性能(低水平和高水平的阳离子型单体)。 Using method AATCC 100-series of cationic polymers (without any additive incorporated into the polymer) Evaluation (low and high levels of cationic monomer) of an anti-bacterial properties. 该聚合物表现出>99%的杀死,而非阳离子型的对照聚合物没有表现出任何杀死。 The polymer exhibits> 99% killing, not a control cationic polymer did not show any kill. 结果和讨论:用于这项研究的抗真菌添加剂表示在表1中。 Results and Discussion: The research for antifungal additives shown in Table 1. 表1 —用于聚合反应的添加剂的列表添加剂名称 化学说明 最初用途 溶解度Amical AF 二碘代曱基甲苯酰基砜 抗真菌剂 棕褐色固体。 Table 1 - List of additives used in chemical names additives initial polymerization explanatory purposes solubility Amical AF diiodo Yue sulfone group toluoyl antifungal tan solid. 有限的单体中溶解度Microban PZ 丙环唑 抗真菌剂 纯净的为蜡状固体。 Limited monomer solubility Microban PZ propiconazole pure antifungal agent as a waxy solid. 极易溶的Microban TZ 戊唑醇 抗真菌剂 白色固体。 The Microban TZ very soluble tebuconazole antifungal agent as a white solid. 极易溶的Microban P2 邻笨基苯盼钠 抗细菌剂 固体。 O Microban P2 pole foolish soluble sodium benzene trypan solid antibacterial agent. 水溶性的三氯生 氯代二苯基醚 抗细菌剂 固体。 Triclosan soluble chlorinated diphenyl ether antibacterial agent solids. 极易溶于单体Microban Z01 吡硫翁锌 抗真菌剂 固体。 Easily soluble monomer Microban Z01 zinc pyrithione antifungal solid. 不溶于单体理想地,所述材料在聚合反应条件过程中不显著反应,因此在聚合反应过程中它们没有降解。 Insoluble monomers Desirably, the material does not significantly react during the polymerization conditions, so they are not degraded in the course of the polymerization reaction. 在一些实施方案中,可以观察到低水平的添加剂,可能是由于降解、或是难以从聚合物胶乳中提取出来。 In some embodiments, low levels of additives can be observed, probably due to degradation, or is difficult to extract from the polymer latex. 在任何情况中,添加剂在胶乳中的保留引起成品纸中保留抗真菌性能。 In any case, the additive remains in the latex causes the finished paper retains antifungal properties. 使用Amical进行的最初的聚合表明,Amical在以相对大的量并入时降解。 Amical used for initial polymerization show, Amical degrade when incorporated in relatively large amounts. 将聚合温度作为降解的可能原因进行研究,并且将其保持在可行的尽可能低的温度(典型地〈7(TC)。在聚合反应结束时对样品进行汽提,直到期望的固体含量。样品的初期试验表示在表2中。所述试验包括ASTM G-21,其中将真菌直接接种在涂层纸样品上,然后在湿度试验室中保持28天。使用# 10 Meyer棒将胶乳涂料施加在纸上,并且纸施加单个涂层。然而,考虑到纸可能没有被充分覆盖,确定了这不是充分的涂层厚度, 并且这反映在图1中所示的霉菌生长数据中。使用PZ/TZ组合物的胶乳样品(MB-38, MB-39)表现出有力的真菌抑制特征。测定从胶乳样品回收的添加剂水平并且与原来接入的添加剂的量进行比较。数据总结在表2中。分析数据40%固体胶乳乳液 在聚合反应中加栽在阳离子型胶乳粒子中的活性剂(基于湿胶乳乳液的重量的ppm) 基于湿胶乳乳液的分析结果(p The polymerization temperature as possible causes of degradation studies, and kept at a temperature as low as possible (typically <7 (TC). The samples were stripped at the end of the polymerization reaction, until the desired solids content. Sample represents the initial test ASTM G-21 comprises in table 2. the test in which the fungus is directly inoculated on the coated paper samples and then maintained in a humidity chamber for 28 days using a # 10 Meyer bar coating is applied in the latex paper, and the paper is applied to a single layer. However, taking into account the paper may not be sufficiently covered, it is not sufficient to determine the thickness of the coating, and this is reflected in the mold shown in FIG. 1 growth data using PZ / TZ the latex composition sample (MB-38, MB-39) exhibited potent fungal inhibition characteristics. Determination of additive levels recovered from the latex samples and the amount of additive compared with access to the original data are summarized in table 2. analysis data 40% solids latex emulsion was added in the polymerization reaction planted in the cationic latex particles of the active agent (based on the weight of the wet latex emulsion ppm) based on the analysis results of the wet latex emulsion (p pra)MB 3 7 (AF) 10000 95MB26 (AF) 4000 38MB19 (AF) 2000 19MB28 (P2/TZ) 1000/1000 14/790MB29 (P2/TZ) 2000/2000 310/330MB 38 (PZ/TZ) 1000/1000 620/620MB 39 (PZ/TZ) 2000/2000 1700/1400MB47 (Z01) 2000 0MB48 (Z01) 楊0 190MB 30 (B) 2000 1600在这个实施例中,即使在聚合过程中以巨大的量加入,Amical仍不充分地并入到胶乳中。回收得到巨大量的PZ/TZ组合物、以及三氯生。还在较短的(7天培养)真菌研究(本文中称为30-III)中复制了在G-21研究中观察到的结果。结果表示在图2中。Microban ZOl、 0.4% (基于湿重)的吡硫翁锌、和PZ/TZ都很好地起作用。30-III真菌试验是基于生产1"X1"的千燥胶乳薄片并且将真菌物质直接接种在样品上,然后在7天之后观察其生长。这时不如G-21试验那么严格的试验,但是给出了添加剂效力的快速指示。在这项试验中,Amical样品表现出一些真菌抑制。在这项试验中,在没有任何添加剂的情况下, pra) MB 3 7 (AF) 10000 95MB26 (AF) 4000 38MB19 (AF) 2000 19MB28 (P2 / TZ) 1000/1000 14 / 790MB29 (P2 / TZ) 2000/2000 310 / 330MB 38 (PZ / TZ) 1000 / 1000 620 / 620MB 39 (PZ / TZ) 2000/2000 1700 / 1400MB47 (Z01) 2000 0MB48 (Z01) Yang 0 190MB 30 (B) 2000 1600 in this embodiment, even in the huge amount added during the polymerization, Amical still not sufficiently incorporated into the latex. recovered huge amount of PZ / TZ compositions, and triclosan. still shorter (7 day culture) fungi (referred to herein as 30-III) copy the results observed in the G-21 study. the results are shown in FIG. 2 .Microban ZOl, 0.4% zinc pyrithione (based on wet weight), and PZ / TZ all function well .30-III fungi test is based on the latex dry in the production of sheet 1 "X1" and the fungal material seeded directly on the sample and then observing its growth after 7 days. at this time inferior G-21 test less stringent test, are given an additive effect the quick indication. in this test, the Amical samples showed some fungal inhibition. in this trial, in the absence of any additives, 离子型聚合物本身不表现出显著的抗真菌性质。阳离子电荷的变化似乎不影响抗真菌性能。这与其中为聚合物薄膜接种真菌物质并且在湿度试验室中留置6个月而没有任何霉菌生长的不同的抗真菌试验形成对比。 Ionic polymers themselves do not exhibit significant anti-fungal properties. Cationic charge change does not seem to affect the antifungal performance. This is where the polymer film and the inoculation fungal material retained for six months in a humidity chamber without any mold growth antifungal test different contrast. 这个结果的一个原因可能是试验的薄膜是比本文中试验的那些更厚的薄膜(约4密耳(mils )或100微米)。 One reason for this may be the result of the test film is a thin film than those tested herein thicker (about 4 mils (mils) or 100 [mu] m). 使用增加的涂层厚度进行试验的第二轮,以便确保完全覆盖纸的 Increase coating thickness using a second test round, in order to ensure complete coverage of the paper

表面。 surface. 涂层的纸样品的第二轮试验根据ASTM D-3273进行。 The second round of testing of coated paper samples carried out according to ASTM D-3273. 在这项研究中,持续时间保持相同(28天),但是不是将真菌物质直接接种在表面上。 In this study, the duration remains the same (28 days), but not the fungal material seeded directly on the surface. 而是将它们作为孢子保持在湿度试验室中,然后像现实世界的情况那样使其落在涂层纸的表面上。 Instead, they are maintained in a humidity chamber as spores, and then as is the case in the real world as it falls on the surface of the coated paper. 这项研究的结果表示在图3中。 The results of this study are shown in Figure 3.

在这项研究中,Amical和PZ/TZ都是有效的,但是Z01没有很好地起作用。 In this study, Amical and PZ / TZ are effective, but Z01 did not work well. 没有任何添加剂的阳离子型聚合物也似乎是没有表现出抗真菌性能,并且似乎是与无涂层的纸样品相似。 Without any additives cationic polymers it seems to be not exhibit anti-fungal properties, and appears to be similar to the uncoated paper samples. 图3中所示的分析数据是基于真菌研究开始之前涂层样品的测量结果。 Analysis of the data shown in Figure 3 is based on measurements of the coated sample before the start of the study of fungi. 从纸回收的添加剂没有定量。 Recovering the additive from the paper is not quantitative.

研究的下一个阶段是要证明可以通过与涂层纸同样的湿部工艺得到相同的性能。 The next phase of the study is to demonstrate that the same performance can be obtained by the same process and the wet coated paper portion. 将胶乳沉积在纸上涉及将固定量的胶乳(基于纤维为10%)沉积在软木纤维上,并对其进行抗真菌评价。 The latex is deposited on the paper involves a fixed amount of latex (10% based on fiber) is deposited on softwood fibers, and subjected to evaluation of the antifungal. 胶乳纸的添加剂的量为约7. 5% (在一个样品纸为2. 5重量% PZ和5重量% TZ)。 The amount of additive latex paper is from about 7.5 percent (on a sample of paper is 2.5 wt% PZ and 5 wt% TZ). 这些数据总结在图4中。 These data are summarized in Figure 4. 在这项研究中,使用有PZ/TZ添加剂(MB-87)和没有PZ/TZ添加剂(MB-86)的阳离子型胶乳生产紙样品。 In this study, there PZ / TZ additive (MB-87) and without PZ / TZ samples cationic latex production of paper additive (MB-86) of. 如前所述,胶乳中的PZ/TZ添加剂的量为~ 7.5% (基于干重)。 As previously mentioned, latex PZ / TZ additive is an amount to 7.5% (based on dry weight). 这样在成品纸中得到约6680 ppm的PZ/TZ和基于纤维基重为10%的聚合物或胶乳。 This gave approximately 6680 ppm in the finished paper PZ / TZ-based fibers and a basis weight of 10% polymer or latex.

还提供了PZ/TZ的分散体(M-3078),其活性为28%。 Also provided PZ / TZ dispersion (M-3078), with an activity of 28%. 将其用作阳离子型胶乳MB-86的后加入(post add),得到实质上相同的PZ/TZ的量。 After it is used as the cationic latex MB-86 was added (post add), to obtain substantially the same as the PZ / TZ, amount. 因此,后加入分散体的样品具有约10%的PZ/TZ浓度,远远超过聚合的胶乳样品的PZ/TZ浓度,并且会在成品纸中产生约9000 ppm 的PZ/TZ浓度。 Thus, the sample was added after dispersion having about 10% of the PZ / TZ concentration of PZ far exceeds polymeric latex samples / TZ concentration of about 9000 ppm and produces a PZ / TZ concentration in the finished paper. 简单的胶乳(MB-86)、具有后加入的PZ/TZ的MB-86聚合的PZ/TZ sample MB-87抗真菌结果表示在图4中。 Simple latex (MB-86), after having added PZ / TZ in the MB-86 polymerized PZ / TZ sample MB-87 Antifungal results are shown in FIG. 4.

正如在涂层样品研究中的情况一样,只有阳离子型胶乳的纸没有通过真菌D-3273试验。 As in the case of the coated sample study, as only cationic latex did not pass the paper fungal D-3273 test. 后加入的和聚合的PZ/TZ样品都通过了试验。 After addition and polymerized PZ / TZ samples passed the test. 需要指出的是,聚合的添加剂样品(MB-87)具有低~ 3000 ppm的PZ/TZ, 但是似乎是仍与后加入样品同样地起作用,或者略更好地起作用。 It should be noted that the polymerized additive sample (MB-87) having a low ~ 3000 ppm of PZ / TZ, but still seemed to be added after the sample acts similarly to or slightly better effect. 没有观察到霉菌生长。 No mold growth was observed. 在说明书中,已经公开了典型的实施方案,并且尽管使用了专用名词,但是它们是以通用的和叙述性的意义使用的,而不是用于限制的目的。 In the specification, there have been disclosed typical embodiments and, although specific terms are employed, they are generic and descriptive sense and not for purposes of limitation. 应该清楚地理解,在阅读本文中的说明之后,本领域技术人员可以想到本发明的各种其它实施方案、方面、改进和等价物,其并 It should be clearly understood that, after reading the description herein, may occur to those skilled in the art that various other embodiments of the invention, aspects, modifications and equivalents, and which

不脱离本发明的精神实质或权利要求的范围。 Without departing from the spirit or scope of the invention as claimed in claims. 提供以下权利要求以确保本申请在所有的管辖区域满足作为优先权申请的所有法定条件,而 The following claims to ensure that all statutory requirements as a priority application of the present application meets all jurisdictions, and

不应该看作是本文中公开的对胶乳组合物、其使用方法、和并入有或 Should not be construed as disclosed herein to latex compositions, methods of use, or incorporate, and

包含胶乳组合物的制品的完整范围的阐述。 Set forth the full scope of compositions comprising a latex article.

Claims (43)

  1. 1.一种生物活性阳离子型聚合物胶乳,其包括: a)包括以下聚合产物的胶乳聚合物,所述聚合产物为:i)至少一种烯属不饱和的第一单体和ii)至少一种烯属不饱和的第二单体的聚合产物,所述第二单体是阳离子型的或是阳离子的前体; b)至少部分地包封在胶乳聚合物内的至少一种生物活性组分;和c)任选的被并入到胶乳聚合物中的至少一种空间体积大的组分。 A bioactive cationic polymer latex comprising: a) a latex polymer comprising the polymerization product, the polymerization product of: i) at least one ethylenically unsaturated first monomer and ii) at least the polymerization product of one ethylenically unsaturated second monomer, said second monomer is cationic or a precursor to a cation; b) at least partially encapsulated within the latex polymer is at least one bioactive component; and c) is optionally incorporated into the latex polymer is at least one component space volume.
  2. 2. 权利要求1的生物活性阳离子型聚合物胶乳,其中所述至少一种烯属不饱和的第一单体独立地选自乙烯基芳香族单体、囟化或非卣化的烯烃单体、脂肪族的共轭二烯单体、非芳香族的不饱和的单或二羧酸酯单体、基于不饱和的二羧酸单体的半酯的单体、不饱和的单或二羧酸单体、含腈单体、环状或无环的含胺单体、支化或非支化的烷基乙烯基酯单体、卣化或非卣化的烷基丙烯酸酯单体、卣化或非卣化的芳基丙烯酸酯单体、羧酸乙烯基酯、乙酸烯基酯、羧酸烯基酯、乙烯基卣化物、偏卣乙烯、或其任何组合,其任一种具有最多20个碳原子。 Bioactive cationic polymer latex of claim 1, wherein the at least one first ethylenically unsaturated monomer is independently selected from vinyl aromatic monomers, halogenated or non-olefin monomers wine container aliphatic conjugated diene monomers, non-aromatic unsaturated mono- or dicarboxylic ester monomers, monomers based on the half ester of unsaturated dicarboxylic acid monomers, unsaturated mono- or dicarboxylic acid monomers, nitrile-containing monomers, cyclic or acyclic amine-containing monomer, a branched or unbranched alkyl vinyl ester monomer, wine container of wine container or alkyl acrylate monomer, wine container of the wine container or non-aryl acrylate monomers, carboxylic acid vinyl esters, acetic acid alkenyl esters, carboxylic acid alkenyl esters, a vinyl compound wine container, ethylene vinylidene wine container, or any combination thereof, any of which having up to 20 carbon atoms.
  3. 3. 权利要求1的生物活性阳离子型聚合物胶乳,其中至少一种烯属不饱和的第一单体独立地选自苯乙烯、对甲基苯乙烯、氯代甲基苯乙烯、 乙烯基甲苯、乙烯、丁二烯、(甲基)丙烯酸曱基酯、(曱基)丙烯酸乙基酯、(甲基)丙烯酸丙基酯、(甲基)丙烯酸丁基酯、(甲基)丙烯酸戊基酉旨、 (曱基)丙烯酸缩水甘油基酯、(甲基)丙烯酸异癸基酯、(曱基)丙烯酸月桂基酯、马来酸单甲酯、衣康酸、(甲基)丙烯腈、(曱基)丙烯酰胺、N-羟甲基(甲基)丙烯酰胺、N-(异丁氧基曱基)(甲基)丙烯酰胺、新癸酸乙烯基酯、叔羧酸乙烯基酯、乙酸乙烯基酯、C广Cs烷基乙烯基醚、C3-C8 烷氧基乙烯基醚、乙烯基氯、偏二氯乙烯、乙烯基氟、1,1-二氟乙烯、 三氟乙烯、四氟乙烯、三氟氯乙烯、六氟丙烯、三氟氯乙烯、全氟丁基乙烯、全氟化的C3-Csa-烯烃、 Bioactive cationic polymer latex of claim 1, wherein the at least one first ethylenically unsaturated monomer is independently selected from styrene, methyl styrene, chloromethyl styrene, vinyl toluene , ethylene, butadiene, (meth) acrylate ester Yue, (Yue-yl) acrylate, (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl unitary purpose, (Yue-yl) acrylate, glycidyl (meth) acrylate, isodecyl acrylate, (Yue-yl) acrylate, lauryl methacrylate, monomethyl maleate, itaconic acid, (meth) acrylonitrile, (Yue-yl) acrylamide, N- methylol (meth) acrylamide, N- (isobutoxy Yue-yl) (meth) acrylamide, vinyl neodecanoate, vinyl esters of versatic acid, vinyl acetate, C Cs alkyl vinyl ether wide, C3-C8 alkoxy vinyl ethers, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrakis vinyl fluoride, chlorotrifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, perfluorobutyl ethylene, perfluorinated C3-Csa- olefins, 化的C广C8烷基乙烯基醚、全氟化的C「C8烷基乙烯基醚、全氟化的CfCs烷氧基乙烯基醚、或其任何组合。 C of the wide C8 alkyl vinyl ether, perfluorinated C "C8 alkyl vinylether, a perfluorinated alkoxy vinyl ether CfCs, or any combination thereof.
  4. 4. 权利要求1的生物活性阳离子型聚合物胶乳,其中至少一种烯属不饱和的第二单体独立地选自胺单体、酰胺单体、季胺单体、磷银单体、锍单体、或其任何组合,其任一种都具有最多20个碳原子。 Bioactive cationic polymer latex of claim 1, wherein the at least one ethylenically unsaturated second monomer are independently selected from amine monomer, an amide monomer, a quaternary amine monomer, silver phosphate monomers, sulfonium monomers, or any combination thereof, any of which having up to 20 carbon atoms.
  5. 5. 权利要求1的生物活性阳离子型聚合物胶乳,其中至少一种烯属不饱和的第二单体独立地选自丙烯酸二甲基氨基乙酯;丙烯酸二乙基氨基乙基酯;甲基丙烯酸二曱基氨基乙基酯;甲基丙烯酸二乙基氨基乙基酯;甲基丙烯酸叔丁基氨基乙基酯;况舲二曱基丙烯酰胺;M 二甲基氨基丙基丙烯酰胺;丙烯酰基吗啉;异丙基丙烯酰胺;《二乙基丙烯酰胺;二甲基氨基乙基乙烯基醚;2-甲基-l-乙烯基咪唑;^ 二曱基-氨基丙基曱基丙烯酰胺;乙烯基吡啶;乙烯基卡基胺;曱基氯化物季铵化的二曱基氨基乙基丙烯酸酯;曱基氯化物季铵化的二曱基氨基乙基甲基丙埽酸酯;二烯丙基二甲基氯化铵;甲基氯化物季铵化的N, N-二甲基氨基丙基丙烯酰胺;三甲基-(乙烯基氧基乙基)氯化铵;l-乙烯基-2, 3-二甲基咪唑错氯化物;乙烯基爷基胺盐酸盐;乙烯基吡啶银盐酸盐; Bioactive cationic polymer latex of claim 1, wherein the at least one ethylenically unsaturated second monomer are independently selected from acrylate, dimethylaminoethyl acrylate; acrylate, diethylaminoethyl acrylate; methyl Yue acrylic acid aminoethyl ester group; methacrylate, diethylaminoethyl acrylate; methacrylate, tert-butylaminoethyl acrylate; Ling two conditions Yue acrylamide; M-dimethylaminopropyl acrylamide; propylene formylmorpholine; isopropyl acrylamide; "diethyl acrylamide; dimethylaminoethyl vinyl ether; -l- methyl-vinylimidazole; ^ yl two Yue - aminopropyl acrylamide Yue ; vinyl pyridine; Ji Kaji ethylene amine; Yue chloride quaternized di Yue acrylate group; Yue chloride quaternized di-methylpropan-aminoethyl group Yue broom ester; two diallyl dimethyl ammonium chloride; the methyl chloride quaternized N, N- dimethylaminopropyl acrylamide; trimethyl - (vinyloxyethyl) ammonium chloride; L-ethylene -2-yl, 3-methylimidazolium chloride error; Ye vinyl-ylamine hydrochloride; silver salts of vinyl pyridine; 其任何组合。 Any combination thereof.
  6. 6. 权利要求1的生物活性阳离子型聚合物胶乳,其中至少一种空间体积大的组分独立地选自至少一种空间体积大的烯属不饱和的第三单体、至少一种空间体积大的聚合物、或其任何组合。 Bioactive cationic polymer latex of at least one volume of space as claimed in claim 6, wherein the at least one sterically bulky component is independently selected from at least one sterically bulky ethylenically unsaturated third monomer, large polymer, or any combination thereof.
  7. 7. 权利要求1的生物活性阳离子型聚合物胶乳,其中至少一种空间体积大的组分为独立地选自以下的至少一种空间体积大的烯属不饱和的第三单体:a)CH2=C(R")COO(CH2CHR"0)mR3A,其中Ru、 R"、和R"独立地选自H 或具有1-6个(含端值)碳原子的烷基基团,并且m为l-30(含端值)的整数;b) CH2=C(R1B)COO(CH2CH20)n(CH2CHR2B0)PR3B,其中R1B、 R2B和R3B独立地选自H或具有1-6个(含端值)碳原子的烷基基团,并且n和p为独立地选自l-15(含端值)的整数;c) CH2=C(Rlc)COO(CH2CHR2C0)q(CH2CH20)rR3C,其中R1C、 R2C和R"虫立地选自H或具有1-6个(含端值)碳原子的烷基基团,并且q和r为独立地选自l-15(含端值)的整数;或d) 其任何组合。 Bioactive cationic polymer latex of claim 1, wherein at least one of a large volume of space of at least one component of a large spatial volume independently selected from ethylenically unsaturated third monomer: a) CH2 = C (R ") COO (CH2CHR" 0) mR3A, wherein Ru, R ", and R" are independently selected from H or from 1 to 6 (inclusive) carbon atoms in the alkyl group, and m is l-30 (inclusive) is an integer; b) CH2 = C (R1B) COO (CH2CH20) n (CH2CHR2B0) pR3B, wherein R1B, R2B and R3B are independently selected from H or from 1 to 6 (inclusive integer value) carbon atom alkyl group, and n and p are independently selected from l-15 (inclusive) of; c) CH2 = C (Rlc) COO (CH2CHR2C0) q (CH2CH20) rR3C, wherein R1C , R2C and r "are selected from H or insect habitats having from 1 to 6 (inclusive) carbon atoms in the alkyl group, and q and r are integers independently selected from l-15 (inclusive); and, or d) any combination thereof.
  8. 8. 权利要求1的生物活性阳离子型聚合物胶乳,其中至少一种空间体积大的组分为独立地选自以下的至少一种空间体积大的烯属不饱和的第三单体:a) CH2=C(R1A)COO(CH2CHR2A0)mR3A,其中R1A、 R"和R"独立地选自H或甲基,并且m为l-10(含端值)的整数;b) CH2=C(R1B)COO(CH2CH20)n(CH2CHR2B0)pR3B,其中R1B、 R2B和R3B独立地选自H或曱基,并且n和p为独立地选自l-10(含端值)的整数;c) CH2=C(Rlc)COO(CH2CHR2C0)q(CH2CH20)rR3C,其中R1C、 R2C、和R"独立地选自H或甲基,并且q和r为独立地选自l-10(含端值)的整数;或d) 其任何組合。 Bioactive cationic polymer latex of claim 1, wherein at least one of a large volume of space of at least one component of a large spatial volume independently selected from ethylenically unsaturated third monomer: a) CH2 = C (R1A) COO (CH2CHR2A0) mR3A, wherein R1A, R "and R" are independently selected from H or methyl, and m is l-10 (inclusive) is an integer; b) CH2 = C (R1B ) COO (CH2CH20) n (CH2CHR2B0) pR3B, wherein R1B, R2B and R3B are independently selected from H or Yue group, and n and p are integers independently selected from l-10 (inclusive) of; c) CH2 = C (Rlc) COO (CH2CHR2C0) q (CH2CH20) rR3C, wherein R1C, R2C, and r "are independently selected from H or methyl, and q and r are independently selected from l-10 (inclusive) of the integer ; or d) any combination thereof.
  9. 9. 权利要求1的生物活性阳离子型聚合物胶乳,其中至少一种空间体积大的组分独立地选自:烷氧基化的二羧酸的单酯;烷氧基化的二羧酸的二酯;聚氧乙烯烷基苯基醚;可聚合的表面活性剂;或其任何组合。 9. The bioactive cationic polymer latex as claimed in claim 1, wherein the at least one sterically bulky component is independently selected from: alkoxylated monoesters of dicarboxylic acids; alkoxylated dicarboxylic acid diesters; polyoxyethylene alkylphenyl ether; polymerizable surfactant; or any combination thereof.
  10. 10. 权利要求1的生物活性阳离子型聚合物胶乳,其中至少一种空间体积大的组分为独立地选自聚乙烯醇、聚乙烯吡咯烷酮、羟基乙基纤维素、或其任何组合的至少一种空间体积大的聚合物。 At least a bioactive cationic polymer latex of claim 10, wherein a large volume of space of at least one component independently selected from polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, or any combination thereof space volume large polymer species.
  11. 11. 权利要求1的生物活性阳离子型聚合物胶乳,其中至少一种生物活性組分独立地选自十一碳烯酸;十一碳烯醇;十一碳烯酸与羟基乙基(曱基)丙烯酸酯或聚乙二醇(曱基)丙烯酸酯的反应产物;十一碳烯醇与(甲基)丙烯酸、马来酐或衣康酸的反应产物;壳聚糖或改性的壳聚糖; 或其任何组合。 11. The bioactive cationic polymer latex as claimed in claim 1, wherein the at least one biologically active component is independently selected from undecylenic acid; undecylenic alcohol; undecylenic acid and hydroxyethyl (Yue-yl ) the reaction product of an acrylate or polyethylene glycol acrylate (Yue-yl); undecylenic alcohol with (meth) acrylic acid reaction product of maleic anhydride or itaconic acid; chitosan or modified chitosan sugar; or any combination thereof.
  12. 12. 权利要求1的生物活性阳离子型聚合物胶乳,其中至少一种生物活性组分独立地选自铜、铜盐、银、银盐、锌、锌盐、氧化银、氧化锌、氯己定、氯己定葡糖酸盐、戊二醛、哈拉宗、六氯酚、呋喃西林、 硝甲酚汞、聚维酮-碘、硫柳汞、d-到Cs-对幾基苯曱酸酯类、次氯酸盐、clofucarban、氯节酚、泊洛沙姆-碘、酚醛树脂、乙酸磺胺米隆、 盐酸氨吖啶、季铵盐、奥昔氯生、美溴沙仑、汞溴红、二溴沙仑、月桂酸甘油酯、吡硫翁盐、吡硫翁钠、吡硫翁锌、(十二烷基)(二亚乙基二胺)甘氨酸、(十二烷基)(氨基丙基)甘氨酸、苯酚、间甲酚、邻曱酚、 对曱酚、邻苯基-苯酚、间苯二酚、乙烯基苯酚、聚合的胍、多粘菌素、杆菌肽、环杆菌素、八肽霉素、溶菌酶、溶葡球菌霉、纤维素酶、万古霉素、利托菌素、类放线菌素、阿伏帕星、短杆菌酪肽A、短 12. The bioactive cationic polymer latex as claimed in claim 1, wherein the at least one biologically active component is independently selected from copper, copper salts, silver, silver salts, zinc, zinc salts, silver oxide, zinc oxide, chlorhexidine , chlorhexidine gluconate, glutaraldehyde, Sahara cases, hexachlorophene, nitrofurazone, nitromersol mercury, povidone - iodine, thimerosal, d- to Yue phenyl ester Cs- several classes, hypochlorite, clofucarban, section chloro phenol, poloxamer - iodine, phenolics, mafenide acetate, ammonia acridine hydrochloride, quaternary ammonium salts, triclosan oxybutynin, US bromo Sharon, merbromin, two bromo Sharon, glyceryl laurate, pyrithione salts, sodium pyrithione, zinc pyrithione, (dodecyl) (diethylenediamine) glycine, (dodecyl) (aminopropyl ) glycine, phenol, m-cresol, o-phenol Yue, Yue of phenol, o-phenyl - phenol, resorcinol, vinyl phenol, polymeric guanidines, polymyxins, bacitracin, bacteriocins ring, octapeptide ADM, lysozyme, lysostaphin mildew, cellulase, vancomycin, ristocetin, like actinomycin, avoparcin, tyrocidines A, short 杆菌肽S、 多氧菌素D、衣霉素、新霉素、链霉素、或其任何组合。 Bacitracin S, polyoxin D, tunicamycin, neomycin, streptomycin, or any combination thereof.
  13. 13. 权利要求1的生物活性阳离子型聚合物胶乳,其中至少一种生物活性组分独立地选自阿扎康唑、联苯三唑醇、溴克座、环丙唑醇、烯峻醇、腈苯喳、氟硅峻、烯菌灵、抑霉喳、imibe腦nazole、叶菌峻、 多效唑、perfuazoate、戊菌哇、珪氟喳、三喳酮、三喳醇、烯效唑、 代森锰锌、代森锰、代森联、代森锌、咯菌睛、氟喹唑、苯醚曱环唑、 4, 5-二甲基-N- (2-丙烯基)-2-(三曱基甲硅烷基)-3-噻吩曱酰胺(硅噻菌胺,sylthiopham)、己唑唑、乙环唑磷、灭菌唑、粉唑醇、氟环唑、 糠菌唑、四氟醚唑、腈菌唑、联苯三唑醇、嘧審胺、嘧菌环胺、十三吗啉、丁苯吗啉、醚菌酯、嗜菌酯、ZEN90160TM、拌种咯、苯霜灵、呋霜灵、甲霜灵、R-甲霜灵、orfurace、喁霜灵、萎锈灵、咪鲜胺、氟菌唑、 啶斑肟、苯并(1,2,3)噻二唑-7-硫代羧酸-S-甲酯、百菌清、霜脲氰、 烯酰吗啉 13. The bioactive cationic polymer latex as claimed in claim 1, wherein the at least one bioactive component A Zhakang independently selected from thiazole, biphenyl triadimenol, bromo g seat, cyproconazole, alkenyl Jun alcohol, nitriles benzene chirp fluorosilicate Jun, alkenyl benomyl, mycophenolate twitter, imibe brain nazole, metconazole Jun, paclobutrazol, perfuazoate, penconazole wow, Gui-fluoro-chirp, three chirp one, three chirp alcohol, uniconazole, zineb MnZn, maneb, metiram, zineb, eye fludioxonil, fluquinconazole, Yue propiconazole ether, 4,5-dimethyl -N- (2- propenyl) 2- (tri Yue silyl) -3-thiophene carboxamide Yue (silthiofam, sylthiopham), hexaconazole oxazole, phosphorus acetate epoxiconazole, triticonazole, flutriafol, epoxiconazole, bromuconazole, cyproconazole tetrafluoro , myclobutanil, triadimenol biphenyl, ethyl amine trial, cyprodinil, tridemorph, fenpropimorph, kresoxim-methyl, azoxystrobin addicted, ZEN90160TM, fenpiclonil, benalaxyl, furosemide Cream Ling, metalaxyl, R- metalaxyl, orfurace, breathing of fish oxadixyl, carboxin, prochloraz, triflumizole, pyrifenox, benzo (1,2,3) thiadiazole-7-sulfur -S- fluorocarboxylic acid methyl ester, chlorothalonil, cymoxanil, dimethomorph 嗜,唑菌酮、苯氧喹啉、苯锈啶、螺环菌胺、咪唑嗪、BAS50001FTM、 p恶霉灵、戊菌隆、咪唑菌酮、双胍辛、苯菌灵、克菌丹、 多菌灵、capropamid、乙嘧酚、氟酰胺、三乙膦酸铝、麦穗宁、hymexanol、 春雷霉素、双胍辛胺-三乙酸盐、种菌唑、异菌脲、灭锈胺、甲霜灵-M、 氟苯嗜啶醇、喹啉铜、喹菌酮、稻瘟酯、盐酸霜霉威、百快隆、五氯硝基苯、硅瘗菌胺、M0NTM 65500、四氯硝基苯、噻菌灵、赛氟灭、曱基疏菌灵、福美双、曱基立枯磷、氟菌唑等、或其任何组合。 Addicted, famoxadone, quinoxyfen, fenpropidin, spiroxamine, triazine imidazole, BAS50001FTM, p hymexazole, pencycuron, fenamidone, Iminoctadine, benomyl, captan, multiple benomyl, capropamid, ethirimol, flutolanil, fosetyl-aluminum, fuberidazole, hymexanol, kasugamycin, iminoctadine - triacetate, ipconazole, iprodione, mepronil, A oxadixyl -M, piperidin-fluorophenyl addicted to alcohol, oxine-copper, oxolinic acid, pefurazoate, propamocarb hydrochloride, one hundred long fast, quintozene, silicon bury bacteria amine, M0NTM 65500, nitro tetrachloro benzene, thiabendazole, flufenamic race, Yue-yl sparse benomyl, thiram, tolclofos-yl Yue, triflumizole, etc., or any combination thereof.
  14. 14. 权利要求1的生物活性阳离子型聚合物胶乳,其包括基于总的单体重量为约20重量%-约99. 5重量%的烯属不饱和的第一单体。 14. The bioactive cationic polymer latex as claimed in claim 1, comprising from about 20 wt% based on the total monomer weight - unsaturated first monomer to about 99.5 wt% of an ethylenically.
  15. 15. 权利要求1的生物活性阳离子型聚合物胶乳,其包括基于总的单体重量为约0. 01重量%-约75重量°/。 15. The bioactive cationic polymer latex as claimed in claim 1, comprising based on the total monomer weight of about 0.01 wt% - about 75 wt ° /. 的烯属不饱和的第二单体。 The second ethylenically unsaturated monomer.
  16. 16. 权利要求1的生物活性阳离子型聚合物胶乳,其包括基于总的单体重量为约0. 01重量°/广约40重量%的生物活性填加剂。 16. The bioactive cationic polymer latex as claimed in claim 1, comprising based on the total monomer weight of about 0.01 wt ° / about 40 wt% broad biological activity fill additives.
  17. 17. 权利要求1的生物活性阳离子型聚合物胶乳,其包括基于总的单体重量为0-约25重量%的空间体积大的组分。 17. The bioactive cationic polymer latex as claimed in claim 1, comprising based on the total monomer weight 0 to about 25% by weight sterically bulky component.
  18. 18. 权利要求1的生物活性阳离子型聚合物胶乳,其进一步包括非离子型表面活性剂。 Bioactive cationic polymer latex as claimed in claim 18, which further comprises a nonionic surfactant.
  19. 19. 权利要求1的生物活性阳离子型聚合物胶乳,其中胶乳聚合物实质上缺乏阳离子型和阴离子型表面活性剂。 19. The bioactive cationic polymer latex as claimed in claim 1, wherein the latex polymer is substantially lack cationic and anionic surfactants.
  20. 20. 包括权利要求1的生物活性阳离子型聚合物胶乳的涂料。 20. comprising a bioactive cationic polymer latex paint of claim 1.
  21. 21. 包括权利要求1的生物活性阳离子型聚合物胶乳的制品。 21 comprises a bioactive cationic polymer latex article of claim 1.
  22. 22. 生产生物活性阳离子型聚合物胶乳的方法,包括在乳液聚合过程中的任何时间引发含水组合物的乳液聚合,所述含水聚合物包括以下组分:a) 至少一种烯属不饱和的第一单体;b) 至少一种烯属不饱和的第二单体,其为阳离子型的或是阳离子的前体5c) 至少一种生物活性组分;d) 至少一种自由基引发剂;e) 任选的至少一种空间体积大的烯属不饱和的第三单体;f) 任选的至少一种空间体积大的聚合物;和g) 任选的至少一种非离子型表面活性剂。 22. A method of producing a bioactive cationic polymer latex comprising any time during the emulsion polymerization initiator aqueous emulsion composition, the aqueous polymer include the following components: a) at least one ethylenically unsaturated a first monomer; b) at least one ethylenically unsaturated second monomer, at least one biologically active component is a cationic or cation precursor 5c); d) at least one free radical initiator ; E) optionally at least one sterically bulky ethylenically unsaturated third monomer; F) optionally at least one of the large spatial volume of the polymer; and g) optionally at least one non-ionic Surfactant.
  23. 23. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中所述方法是半连续工艺,并且其中在乳液聚合过程中的任何时间将至少一种生物活性组分溶解于单体原料中。 The method of producing a bioactive cationic polymer latex of claim 22, wherein said method is semi-continuous process, and wherein at any time during the emulsion polymerization of at least one biologically active ingredient is dissolved in the monomer feed .
  24. 24. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中所述方法是分批工艺,并且其中在乳液聚合的种子阶段存在有至少一种生物活性组分。 Production of bioactive cationic polymer latex is 22 to 24. The method of claim, wherein said method is a batch process, and wherein the at least one biologically active component is present in the seed stage of the emulsion polymerization there.
  25. 25. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中在引发乳液聚合之前将含水组合物组分和至少一种生物活性组分作为分散体提供。 The method of producing biologically active claims 22 to 25. The cationic polymer latex, wherein prior to initiating the emulsion polymerization the aqueous composition components and the at least one biologically active components are provided as a dispersion.
  26. 26. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中至少一种烯属不饱和的第一单体独立地选自乙烯基芳香族单体、卣化或非卣化的烯烃单体、脂肪族的共轭二烯单体、非芳香族的不饱和的单或二羧酸酯单体、基于不饱和的二羧酸单体的半酯的单体、不饱和的单或二羧酸单体、含腈单体、环状或无环的含胺单体、支化或非支化的烷基乙烯基酯单体、卣化或非囟化的烷基丙烯酸酯单体、卣化或非卣化的芳基丙烯酸酯单体、羧酸乙烯基酯、乙酸烯基酯、羧酸烯基酯、乙烯基卣化物、偏卣乙烯、或其任何組合,其任一种具有最多20个碳原子。 The method of producing a bioactive cationic polymer latex as claimed in claim 26. 22, wherein the at least one first ethylenically unsaturated monomer is independently selected from vinyl aromatic monomers, wine container or non-mono olefins wine container thereof, aliphatic conjugated diene monomers, non-aromatic unsaturated mono- or dicarboxylic ester monomers, monomers based on the half ester of unsaturated dicarboxylic acid monomers, unsaturated mono- or di carboxylic acid monomers, nitrile-containing monomers, cyclic or acyclic amine-containing monomer, a branched or unbranched alkyl vinyl ester monomer, wine container or non-halogenated alkyl acrylate monomer, wine container of wine container or non-aryl acrylate monomers, carboxylic acid vinyl esters, acetic acid alkenyl esters, carboxylic acid alkenyl esters, a vinyl compound wine container, ethylene vinylidene wine container, or any combination thereof, any of which having up to 20 carbon atoms.
  27. 27. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中至少一种烯属不饱和的第一单体独立地选自苯乙烯、对曱基苯乙烯、氯代甲基苯乙烯、乙烯基甲苯、乙烯、丁二烯、(甲基)丙烯酸甲基酯、(甲基)丙烯酸乙基酯、(曱基)丙烯酸丙基酯、(曱基)丙烯酸丁基酯、(甲基) 丙烯酸戊基酯、(甲基)丙烯酸缩水甘油基酯、(甲基)丙烯酸异癸基酯、 (曱基)丙烯酸月桂基酯、马来酸单曱酯、衣康酸、(曱基)丙烯腈、(曱基)丙烯酰胺、N-羟甲基(甲基)丙烯酰胺、N-(异丁氧基甲基)(甲基) 丙烯酰胺、新癸酸乙埽基酯、叔羧酸乙烯基酯、乙酸乙烯基酯、C3-C8 烷基乙烯基醚、Cr-C8烷氧基乙烯基醚、氯乙烯、偏二氯乙烯、氟乙烯基、 1,1-二氟乙烯、三氟乙烯、四氟乙烯、三氟氯乙烯、六氟丙烯、三氟氯乙埽、全氟丁基乙烯、全氟化的C3-C The method of producing biologically active claims 22 to 27. A cationic polymer latex, wherein at least one first ethylenically unsaturated monomer is independently selected from styrene, p-Yue group styrene, chloromethyl styrene, vinyl toluene, ethylene, butadiene, (meth) acrylate, (meth) acrylate, (Yue-yl) acrylate, propyl (Yue-yl) acrylate, butyl (meth) acrylate, amyl acrylate, (meth) acrylate, glycidyl (meth) acrylate, isodecyl acrylate, (Yue-yl) acrylate, lauryl methacrylate, maleic acid monoethyl ester Yue, itaconic acid, (Yue-yl) acrylamide nitriles, (Yue-yl) acrylamide, N- methylol (meth) acrylamide, N- (isobutoxymethyl) (meth) acrylamide, neodecanoic acid ethyl ester broom, vinyl versatate ester, vinyl acetate, C3-C8 alkyl vinyl ether, Cr-C8 alkoxy vinyl ether, vinyl chloride, vinylidene chloride, vinyl fluoride vinyl, vinylidene fluoride, trifluoroethylene , tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, chlorotrifluoroethylene broom, perfluorobutyl ethylene, perfluorinated C3-C soc-烯烃、氟化的C3-Cs烷基乙烯基醚、全氟化的C「C8烷基乙烯基醚、全氟化的C3-Cs烷氧基乙烯基醚、其任何组合。 soc- olefins, fluorinated C3-Cs alkyl vinyl ether, perfluorinated C "C8 alkyl vinylether, a perfluorinated C3-Cs alkoxy vinyl ether, and any combination thereof.
  28. 28. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中至少一种烯属不饱和的第二单体独立地选自胺单体、酰胺单体、季胺单体、磷错单体、锍单体、或其任何组合,其任一种都具有最多20个碳原子。 The method of producing biologically active claims 22 to 28. A cationic polymer latex, wherein the at least one ethylenically unsaturated second monomer are independently selected from amine monomer, an amide monomer, a quaternary amine monomer, phosphorus wrong one body, sulfonium monomer, or any combination thereof, any of which having up to 20 carbon atoms.
  29. 29. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中至少一种烯属不饱和的第二单体独立地选自丙烯酸二甲基氨基乙基酯; 丙烯酸二乙基氨基乙基酯;甲基丙烯酸二甲基氨基乙基酯;甲基丙烯酸二乙基氨基乙基酯;甲基丙烯酸叔丁基氨基乙基酯;M ^二曱基丙烯酰胺;乂W-二曱基氨基丙基丙烯酰胺;丙烯酰基吗啉;^-异丙基丙烯酰胺;^ 二乙基丙烯酰胺;二甲基氨基乙基乙烯基醚;2-曱基-l-乙烯基咪唑;W #-二甲基-氨基丙基曱基丙烯酰胺;乙烯基吡咬;乙烯基苄基胺;甲基氯化物季铵化的丙烯酸二曱基氨基乙基酯;曱基氯化物季铵化的甲基丙烯酸二甲基氨基乙基酯;二烯丙基二曱基氯化铵;曱基氯化物季铵化的N, N-二曱基氨基丙基丙烯酰胺;三甲基-(乙烯基氧基乙基)氯化铵;1-乙烯基-2, 3-二甲基咪唑铕氯化物;乙烯基卡基胺盐酸盐;乙烯基 The method of producing a biologically active 22 29. The cationic polymer latex as claimed in claim, wherein the at least one ethylenically unsaturated second monomer are independently selected from acrylate, dimethylaminoethyl methacrylate; diethylaminoethyl acrylate; methacrylic acid dimethylaminoethyl ester; methacrylate, diethylaminoethyl acrylate; methacrylate, tert-butylaminoethyl acrylate; M ^ two Yue acrylamide; amino group qe W- two Yue acrylamide; acryloyl morpholine; ^ - isopropyl acrylamide; ^ diethyl acrylamide; dimethylaminoethyl vinyl ether; Yue-yl -l- 2- vinylimidazole; W # - two methyl - aminopropyl acrylamide Yue; bite vinylpyridine; vinyl benzyl amine; methyl chloride quaternized acrylic acid ethyl ester Yue group; Yue chloride quaternized methacrylate dimethylaminoethyl acrylate; Yue diallyldimethyl ammonium chloride; Yue chloride quaternised N, N- two Yue amidopropyl acrylamide; trimethyl - (vinyloxy b yl) ammonium chloride; 1-vinyl-2,3-dimethyl-imidazol-europium chloride; vinyl Ji Kaji hydrochloride; vinyl 吡啶错盐酸盐;或其任何组合。 -Pyridine hydrochloride; or any combination thereof.
  30. 30. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中至少一种空间体积大的组分独立地选自至少一种空间体积大的烯属不饱和的第三单体、至少一种空间体积大的聚合物、或其任何组合。 The method of producing a bioactive cationic polymer latex as claimed in claim 30. 22, wherein the at least one sterically bulky component is independently selected from at least one sterically bulky ethylenically unsaturated third monomer, at least one of species space bulky polymer, or any combination thereof.
  31. 31. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中至少一种空间体积大的组分为独立地选自以下的至少一种空间体积大的烯属不饱和的笫三单体:a) CH2=C(R1A)COO(CH2CHR2A0)fflR3A,其中R1A、 11"和113"独立地选自H或具有1-6个(含端值)碳原子的烷基基团,并且m为1-30(含端值)的整数;b) CH2=C(R1B)COO(CH2CH20)n(CH2CHR2B0)pR、其中R1B、 R2B和R化独立地选自H或具有1-6个(含端值)碳原子的烷基基团,并且n和p为独立地选自l-15(含端值)的整数;c) CH2=C(Rlc)COO(CH2CHR2C0)q(CH2CH20)rR3C,其中R1C、 R2C和R"虫立地选自H或具有1-6个(含端值)碳原子的烷基基团,并且q和r为独立地选自l-15(含端值)的整数;或d) 其任何组合。 The method of producing a bioactive cationic polymer latex as claimed in claim 31. 22, wherein at least one of a large volume of space of at least one component of a large spatial volume independently selected from ethylenically unsaturated termonomer Zi : a) CH2 = C (R1A) COO (CH2CHR2A0) fflR3A, wherein R1A, 11 "and 113" are independently selected from H or has from 1 to 6 (inclusive) carbon atoms in the alkyl group, and m is integer (inclusive) of 1-30; b) CH2 = C (R1B) COO (CH2CH20) n (CH2CHR2B0) pR, wherein R1B, R2B and of R is independently selected from H or has from 1 to 6 (inclusive integer value) carbon atom alkyl group, and n and p are independently selected from l-15 (inclusive) of; c) CH2 = C (Rlc) COO (CH2CHR2C0) q (CH2CH20) rR3C, wherein R1C , R2C and r "are selected from H or insect habitats having from 1 to 6 (inclusive) carbon atoms in the alkyl group, and q and r are integers independently selected from l-15 (inclusive); and, or d) any combination thereof.
  32. 32. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中至少一种空间体积大的组分为独立地选自以下的至少一种空间体积大的烯属不饱和的第三单体:a)CH2=C(R1A)COO(CH2CHR2A0)mR3A,其中R1A、 R"和R"独立地选自H或甲基,并且m为l-10(含端值)的整数;b) CH2=C(R]B)COO(CH2CH20)n(CH2CHR2B0)pR3B,其中R1B、 R2B和R"独立地选自H或甲基,并且n和p为独立地选自l-10(含端值)的整数;c) CH2=C(Rlc)COO(CH2CHR2C0)q(CH2CH20)rR3C,其中R1C、 R2C和R3C独立地选自H或甲基,并且q和r为独立地选自l-10(含端值)的整数;或d) 其任何组合。 The method of producing a bioactive cationic polymer latex as claimed in claim 32. 22, wherein at least one of a large volume of space of at least one component of a large spatial volume independently selected from ethylenically unsaturated third monomer : a) CH2 = C (R1A) COO (CH2CHR2A0) mR3A, wherein R1A, R "and R" are independently selected from H or methyl, and m is an integer of l-10 (inclusive) of; b) CH2 = C (R] B) COO (CH2CH20) n (CH2CHR2B0) pR3B, wherein R1B, R2B and R "are independently selected from H or methyl, and n and p are independently selected from l-10 (inclusive) of an integer; c) CH2 = C (Rlc) COO (CH2CHR2C0) q (CH2CH20) rR3C, wherein R1C, R2C and R3C are independently selected from H or methyl, and q and r are independently selected from l-10 (inclusive value) is an integer; or d) any combination thereof.
  33. 33. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中至少一种空间体积大的组分独立地选自:烷氧基化的二羧酸的单酯;烷氧基化的二羧酸的二酯;聚氧乙烯烷基苯基醚;可聚合的表面活性剂; 或其任:何組合。 The method of producing a bioactive cationic polymer latex of claim 33. 22, wherein the at least one sterically bulky component is independently selected from: alkoxylated monoesters of dicarboxylic acids; alkoxylated di acid diester; polyoxyethylene alkylphenyl ether; polymerizable surfactant; or any: any combination thereof.
  34. 34. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中至少一种空间体积大的组分为独立地选自聚乙烯醇、聚乙烯吡咯烷酮、 羟基乙基纤维素或其任何组合的至少一种空间体积大的聚合物。 The method of producing a bioactive cationic polymer latex 22 polyvinylpyrrolidone, hydroxyethyl cellulose, or any combination thereof as claimed in claim 34, wherein a large volume of space of at least one component independently selected from polyvinyl alcohol, polymer is at least one sterically volume.
  35. 35. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中至少一种生物活性组分独立地选自十一碳烯酸;十一碳烯醇;十一碳烯酸与羟基乙基(甲基)丙烯酸酯或聚(甲基)丙烯酸乙二醇酯的反应产物;十一碳烯醇与(甲基)丙烯酸、马来酸酐或衣康酸的反应产物;壳聚糖或改性的壳聚糖;或其任何组合。 The method of producing a biologically active 22 35. The cationic polymer latex as claimed in claim, wherein the at least one biologically active component is independently selected from undecylenic acid; undecylenic alcohol; undecylenic acid and hydroxyethyl (meth) acrylate or the reaction product of poly (meth) acrylate esters of ethylene glycol; undecylenic alcohol with (meth) acrylic acid reaction product of maleic anhydride or itaconic acid; chitosan or modified chitosan; or any combination thereof.
  36. 36. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中至少一种生物活性组分独立地选自铜、铜盐、银、银盐、锌、锌盐、氧化银、氧化锌、氯己定、氯己定葡糖酸盐、戊二醛、哈拉宗、六氯酚、 呋喃西林、硝曱酚汞、聚维酮-碘、硫柳汞、C「到C5-对羟基苯甲酸酯、 次氯酸盐、clofucarban、氯千酚、泊洛沙姆-械、酚醛树脂、乙酸磺胺米隆、盐酸氨吖啶、季铵盐、奥昔氯生、美溴沙仑、汞溴红、二溴沙仑、 月桂酸甘油酯、吡疏翁盐、吡硫翁钠、吡疏翁锌、(十二烷基)(二亚乙基二胺)甘氨酸、(十二烷基)(氨基丙基)甘氨酸、苯酚、间甲酚、邻甲酚、对甲酚、邻苯基-苯酚、间苯二酚、乙烯基苯酚、聚合的胍、多粘菌素、杆菌肽、环杆菌素、八肽霉素、溶菌酶、溶葡球菌霉、纤维素酶、万古霉素、利托菌素、类放线菌素、阿伏帕星、短杆 The method of producing biologically active claims 22 to 36. A cationic polymer latex, wherein the at least one biologically active component is independently selected from copper, copper salts, silver, silver salts, zinc, zinc salts, silver oxide, zinc oxide, chlorhexidine, chlorhexidine gluconate, glutaraldehyde, Sahara cases, hexachlorophene, nitrofurazone, nitro phenol mercury Yue, povidone - iodine, thimerosal, C "to C5- parabens , hypochlorite, clofucarban, one thousand chloro phenol, poloxamer - mechanical, phenol resins, mafenide acetate, ammonia acridine hydrochloride, quaternary ammonium salts, triclosan oxybutynin, US bromo Sharon, merbromin, dibromo Sharon, glyceryl laurate, pyrazolyl sparse onium salts, sodium pyrithione, zinc pyrithione sparse pyrazole, (dodecyl) (diethylenediamine) glycine, (dodecyl) (aminopropionate yl) glycine, phenol, m-cresol, o-cresol, p-cresol, o-phenyl - phenol, resorcinol, vinyl phenol, polymeric guanidines, polymyxins, bacitracin, bacteriocins ring, eight ADM peptide, lysozyme, lysostaphin mildew, cellulase, vancomycin, ristocetin, like actinomycin, avoparcin, short game 酪肽A、短杆菌肽S、多氧菌素D、衣霉素、新霉素、链霉素、或其任何组合。 Casein peptide A, gramicidin S, polyoxin D, tunicamycin, neomycin, streptomycin, or any combination thereof.
  37. 37. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中至少一种生物活性组分独立地选自阿扎康唑、联苯三唑醇、溴克座、环丙哇醇、烯唑醇、腈苯喳、氟珪喳、烯菌灵、抑霉唑、imibenconazole、 叶菌唑、多效唑、稻痘酯、戊菌唑、珪氟唑、三唑酮、三哇醇、烯效哇、 代森锰锌、代森锰、代森联、代森锌、咯菌睛、氟喹唑、苯醚甲环唑、 4, 5-二甲基-N- (2-丙烯基)-2- (三甲基甲硅烷基)-3-噻吩甲酰胺(硅噻菌胺,sylthiopham)、己唑唑、乙环嗤磷、灭菌唑、粉唑醇、氟环哇、 糠菌唑、四氟醚唑、腈菌唑、联苯三唑醇、嘧霉胺、嘧菌环胺、十三吗啉、丁苯吗啉、醚菌酯、嘧菌酯、ZEN90160TM、拌种咯、苯霜灵、呋霜灵、甲霜灵、R-甲霜灵、甲呋酰胺、噁霜灵、萎锈灵、咪鲜胺、氟菌唑、 啶斑肟、苯并(1,2,3)噻二唑-7-硫代羧酸-S-曱酯、百菌清、霜 The method of producing a bioactive cationic polymer latex as claimed in claim 37. 22, wherein the at least one bioactive component A Zhakang independently selected from thiazole, biphenyl triadimenol, bromo g seat, cyclopropylmethyl wow alcohol, allyl cyproconazole, nitrile benzene cha, cha-fluoro-Gui, alkenyl benomyl, imazalil, imibenconazole, metconazole, paclobutrazol, rice pox ester, penconazole, Gui-fluoro-oxazole, triadimefon, tri- wow alcohol, allyl effect wow , mancozeb, maneb, metiram, zineb, eye fludioxonil, fluquinconazole, difenoconazole yl, 4,5-dimethyl -N- (2- propenyl) -2 - (trimethylsilyl) -3-thiophenecarboxamide (silthiofam, sylthiopham), hexaconazole oxazole, b ring laugh phosphorus, triticonazole, flutriafol, wow-fluoro-ring, bromuconazole, tetrakis fluoro difenoconazole, myclobutanil, triadimenol biphenyl, pyrimethanil, cyprodinil, tridemorph, fenpropimorph, kresoxim-methyl, azoxystrobin, ZEN90160TM, fenpiclonil, benalaxyl , furalaxyl, metalaxyl, R- metalaxyl, ofurace, oxadixyl, carboxin, prochloraz, triflumizole, pyrifenox, benzo (1,2,3) thiadiazole -S- Yue-7-thiocarboxylate ester, chlorothalonil, cream 脲氰、 烯酰吗啉、噁唑菌酮、苯氧会啉、苯锈啶、螺环菌胺、咪唑嚷、 BAS50001FTM、喁霉灵、戊菌隆、咪唑菌酮、双胍辛、苯菌灵、克菌丹、 多菌灵、capropamid、乙嘧酚、氟酰胺、三乙膦酸铝、麦穗宁、喁霉灵、 春雷霉素、双胍辛胺-三乙酸盐、种菌唑、异菌脲、灭锈胺、曱霜灵-M(精甲霜灵,mefenoxam)、氟苯嘧啶醇、会啉铜、喹菌酮、稻瘋酯、盐酸霜霉威、百快隆、五氟硝基苯、硅噻菌胺、MON™65500、四氯硝基苯、噻菌灵、赛氟灭、甲基硫菌灵、福美双、甲基立枯磷、氟菌唑等、或其任何组合。 Cymoxanil, dimethomorph, famoxadone, phenoxy will morpholine, fenpropidin, spiroxamine, imidazole cried, BAS50001FTM, breathing of fish mold Ling, pencycuron, fenamidone, Iminoctadine, benomyl , captan, carbendazim, capropamid, ethirimol, flutolanil, fosetyl-aluminum, fuberidazole, breathing of fish mold Ling, kasugamycin, iminoctadine - triacetate, ipconazole, iso iprodione, mepronil, Yue oxadixyl -M (metalaxyl, mefenoxam), nuarimol, would-copper, oxolinic acid, ester rice mad, propamocarb hydrochloride, one hundred long fast, five flunitrazepam benzene, silthiofam, MON ™ 65500, tecnazene, thiabendazole, flufenamic race, thiophanate-methyl, thiram, tolclofos-methyl, triflumizole, etc., or any combination thereof .
  38. 38. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中所述生物活性阳离型聚合物胶乳包括基于总的单体重量为约20-约99. 5 重量%的烯属不饱和的第一单体。 The method of producing biologically active claims 22 to 38. Cationic polymer latex, wherein the bioactive cationic polymer latex comprising, based on total weight of the unsaturated monomer is from about 20 to about 99.5 wt% of an ethylenically a first monomer.
  39. 39. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中所述生物活性阳离型聚合物胶乳包括基于总的单体重量为约0. 01-约75 重量%的烯属不饱和的第二单体。 The method of producing biologically active claims 22 to 39. Cationic polymer latex, wherein the bioactive cationic polymer latex comprising, based on total weight of the unsaturated monomer is from about 0.5 to about 01- 75 wt% of an ethylenically the second monomer.
  40. 40. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中所述生物活性阳离型聚合物胶乳包括基于总的单体重量为约O. 01-约40 重量°/。 The method of producing biologically active claims 22 to 40. A cationic polymer latex, wherein the bioactive cationic polymer latex comprises from about 40 to about O. 01- by weight based on the total monomer weight ° /. 的生物活性填加剂。 Biological activity filled with PPD.
  41. 41. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中所述生物活性阳离型聚合物胶乳包括基于总的单体重量为0-约25重量%的空间体积大的组分。 The method of producing biologically active claims 22 to 41. Cationic polymer latex, wherein the bioactive cationic polymer latex comprising, based on total monomer weight 0 to about 25% by weight sterically bulky component.
  42. 42. 权利要求22的生产生物活性阳离子型聚合物胶乳的方法,其中生物活性胶乳聚合物基本上缺乏阳离子型和阴离子型表面活性剂。 The method of producing a bioactive cationic polymer latex as claimed in claim 42. 22, wherein the latex polymer is substantially devoid of biological activity of cationic and anionic surfactants.
  43. 43. 生产生物活性阳离子型聚合物胶乳的方法,包括a) 提供含水组合物,所述组合物包括:i) 至少一种烯属不饱和的第一单体;ii) 至少一种烯属不饱和的第二单体,其为阳离子型的或是阳离子的前体;iii) 任选的至少一种空间体积大的烯属不饱和的第三单体;iv) 至少一种自由基引发剂;和v) 任选的至少一种非离子型表面活性剂;b) 引发该组合物的乳液聚合;和c) 在乳液聚合工艺过程中向组合物中添加至少一种生物活性组分。 43. A method of producing a bioactive cationic polymer latex comprising a) providing an aqueous composition, said composition comprising: i) at least one ethylenically unsaturated first monomer; ii) at least one ethylenically unsaturated unsaturated second monomer that is cationic or a precursor to a cation; iii) optionally at least one sterically bulky ethylenically unsaturated third monomer; IV) at least one free radical initiator ; and v) optionally at least one non-ionic surfactant; b) the polymerization initiator composition; and c) adding at least one bioactive component to the composition during the emulsion polymerization process.
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